JP2003334424A - Gas cleaning method and apparatus therefor - Google Patents
Gas cleaning method and apparatus thereforInfo
- Publication number
- JP2003334424A JP2003334424A JP2002144716A JP2002144716A JP2003334424A JP 2003334424 A JP2003334424 A JP 2003334424A JP 2002144716 A JP2002144716 A JP 2002144716A JP 2002144716 A JP2002144716 A JP 2002144716A JP 2003334424 A JP2003334424 A JP 2003334424A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- filter
- photocatalyst
- gas purifying
- granular photocatalyst
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000004140 cleaning Methods 0.000 title claims abstract description 14
- 239000011941 photocatalyst Substances 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 17
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 17
- 231100000719 pollutant Toxicity 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims description 12
- 230000035939 shock Effects 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 52
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 76
- 239000004408 titanium dioxide Substances 0.000 description 23
- 238000004332 deodorization Methods 0.000 description 14
- 230000001877 deodorizing effect Effects 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- -1 trichlorethylene Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 101001062854 Rattus norvegicus Fatty acid-binding protein 5 Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000011045 prefiltration Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Treating Waste Gases (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、粒状の光触媒を利
用した汚染ガスの浄化方法および浄化装置に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for purifying pollutant gas using a granular photocatalyst.
【０００２】[0002]
【従来の技術】二酸化チタン等、光触媒の有する強い酸
化、還元作用を利用した気体の浄化装置が公知であり、
光触媒は各種汚染気体の清浄化以外にも、脱臭、滅菌等
の用途に利用されている。脱臭装置としては、光触媒を
担持したセラミックスフィルターに悪臭ガスを通過さ
せ、このセラミックスフィルターに紫外線を照射して光
触媒を活性化させ、以て、悪臭ガスを分解・脱臭する装
置が実用化されている。また、トリクロロエチレンとい
った有機塩素化合物を含む汚染ガスの浄化装置として、
円筒状ユニットに構成したガラス繊維基材上に光触媒を
固定し、該ユニットの中心部に紫外線灯を設置し、前記
汚染ガスをこのユニットに通すことによって汚染ガスを
分解・浄化する装置も実用化されている。2. Description of the Related Art A gas purification device utilizing the strong oxidation and reduction effects of a photocatalyst such as titanium dioxide is known.
Photocatalysts are used for deodorization, sterilization, etc. in addition to cleaning various pollutant gases. As a deodorizing device, a device that passes a malodorous gas through a ceramic filter carrying a photocatalyst, irradiates the ceramics filter with ultraviolet rays to activate the photocatalyst, and decomposes and deodorizes the malodorous gas has been put into practical use. . In addition, as a device for purifying polluted gases containing organic chlorine compounds such as trichlorethylene,
Practical application of a device that decomposes and purifies pollutant gas by fixing the photocatalyst on the glass fiber substrate configured in a cylindrical unit, installing an ultraviolet lamp in the center of the unit, and passing the pollutant gas through this unit Has been done.
【０００３】しかしながら、上記殆どの実用化された浄
化装置では、光触媒活性を有する二酸化チタンは、ハニ
カムフィルターや平板状のフィルターの表面に担持また
はバインダーで塗布されていることから、次の点が隘路
となっている。
担体である平板面に紫外線を照射する際、照射効率
が悪く、所要の浄化（脱臭）性能を得るためには、大き
な担体面積が必要となる。
平板面に紫外線を均一にむらなく照射するために、
低圧紫外線ランプが一般に使用されており、出力の小さ
いランプを数十本並べることから、ランプの照射光を有
効に利用することが難しい。より具体的には、１０ｍ3
／分の処理装置では４０Ｗのランプを８０本使用してお
り、照射効率は５０％程度未満である。
低圧灯の寿命は７０００時間程度であり、上記数十
本のうちで不具合や不点灯が生じる可能性が高く、交換
も煩雑である。また、ランプの使用に適した温度条件は
通常、１０〜５０℃の範囲であり、高温ガスの処理には
適さない。
前記フィルター材にダストやミストが付着し、照射
光が遮断されたり、ガス接触が不十分となる。更に、こ
れを防止するために、ガス導入口の手前にフィルターを
設置するなどの対策も必要となる。
前記フィルター材に対する光照射深さは１０数ｍｍ
であり、ガス空塔速度に対して反応時間を稼ぐことがで
きず、１パスでの脱臭性能が悪い。このために、複数段
の処理を行う必要があり、プレフィルター、整流スペー
ス、ランプ配置、光触媒担体等の構成により、装置が大
型化し、設置スペースも広がらざるを得ない。
前記した防塵用フィルターや多本数ランプの交換作
業、さらに、高価な光触媒担持フィルターの汚染劣化に
よる交換作業など、保守作業も容易ではない。However, in most of the above practically used purifying devices, titanium dioxide having photocatalytic activity is carried on the surface of a honeycomb filter or a flat filter or coated with a binder, and therefore the following points are bottlenecked. Has become. When the flat plate surface which is the carrier is irradiated with ultraviolet rays, the irradiation efficiency is poor, and a large carrier area is required to obtain the required purification (deodorization) performance. In order to irradiate the flat surface with ultraviolet rays evenly,
Low-pressure ultraviolet lamps are generally used, and dozens of low-output lamps are arranged, so it is difficult to effectively use the irradiation light of the lamps. More specifically, 10 m 3
The processing device uses 80 40 W lamps and the irradiation efficiency is less than about 50%. The life of the low-pressure lamp is about 7,000 hours, and there is a high possibility that malfunction or non-lighting will occur among the above tens of lamps, and replacement will be complicated. Further, the temperature condition suitable for using the lamp is usually in the range of 10 to 50 ° C., which is not suitable for the treatment of high temperature gas. Dust or mist adheres to the filter material, the irradiation light is blocked, and gas contact becomes insufficient. Furthermore, in order to prevent this, it is necessary to take measures such as installing a filter in front of the gas inlet. The light irradiation depth on the filter material is 10 mm or more.
Therefore, the reaction time cannot be earned against the gas superficial velocity, and the deodorizing performance in one pass is poor. For this reason, it is necessary to perform a plurality of stages of processing, and due to the configuration of the pre-filter, the rectifying space, the lamp arrangement, the photocatalyst carrier, etc., the device becomes large and the installation space must be widened. Maintenance work such as the replacement work of the dustproof filter and the multiple lamps, and the replacement work of the expensive photocatalyst-carrying filter due to contamination deterioration is not easy.
【０００４】特開平１０−３１４５４３号公報には、脱
臭前の被処理空気が下部から送り込まれ、脱臭後の処理
空気が上部から送り出される脱臭塔と、脱臭塔の上部か
ら内部に供給され、重力により下方へ移動しつつ前記被
処理空気中の悪臭ガス成分を吸着して前記脱臭を行う二
酸化チタン粒子と、前記脱臭塔の下方へ移動した二酸化
チタン粒子を取り込み吸着性を再生させた後に脱臭塔の
上部へ戻し供給する再生塔と、再生塔の内部に設けら
れ、二酸化チタン粒子に吸着された悪臭ガス成分を光エ
ネルギで酸化分解して前記吸着性の再生を行うブラック
ライト照明器と、二酸化チタン粒子の前記取り込みと供
給を行う粒体搬送装置とを備えた光触媒流動循環式脱臭
装置が開示されている。当該脱臭装置における再生塔の
内部では二酸化チタン粒子が流動用空気により浮遊させ
られると共に、前記ブラックライト照明器からの紫外線
照射により、その吸着能が再生される。In Japanese Unexamined Patent Publication No. 10-314543, the air to be treated before deodorization is fed from the lower part, and the treated air after deodorization is fed from the upper part, and is supplied to the inside from the upper part of the deodorizing tower, and gravity is applied. The titanium dioxide particles for adsorbing the malodorous gas component in the air to be treated to deodorize while moving downward by the titanium dioxide particles that have moved to the lower part of the deodorization tower and regenerated the adsorptivity and then the deodorization tower A regeneration tower for feeding back to the upper part, a black light illuminator provided inside the regeneration tower for performing oxidative decomposition of the malodorous gas component adsorbed on the titanium dioxide particles with light energy to regenerate the adsorptive property, A photocatalyst fluidized circulation type deodorizing device provided with a granular material conveying device for taking in and supplying the titanium particles is disclosed. Inside the regeneration tower in the deodorizing device, the titanium dioxide particles are suspended by the flowing air, and the adsorption capacity thereof is regenerated by the ultraviolet irradiation from the black light illuminator.
【０００５】しかしながら、上記特開平１０−３１４５
４３号公報記載の発明は、先ず二酸化チタン粒子用の再
生塔を用意する必要がある他、ブラックライト照明器は
紫外線出力が低いという構成装置上の問題点を有してい
る。また、当該公報記載の発明では、直径が１．４〜
２．０ｍｍという大粒径の二酸化チタン粒子を使用して
いるので光照射効率が悪く、触媒反応の点でも課題が残
されている。However, the above-mentioned Japanese Unexamined Patent Publication No. 10-3145.
In the invention described in Japanese Patent Publication No. 43, it is necessary to first prepare a regenerating tower for titanium dioxide particles, and the black light illuminator has a problem in the constituent device that the ultraviolet light output is low. In the invention described in the publication, the diameter is 1.4 to
Since the titanium dioxide particles having a large particle size of 2.0 mm are used, the light irradiation efficiency is poor, and a problem remains in terms of catalytic reaction.
【０００６】また、特開平１０−３１４５４４号公報に
は、脱臭前の被処理空気が下部から送り込まれ、脱臭後
の処理空気が上部から送り出される脱臭塔と、脱臭塔の
上部から内部に供給され、前記被処理空気中の悪臭ガス
成分を吸着して脱臭を行う二酸化チタン粒子と、脱臭塔
内部の上下に多段に設けられ、上部からの二酸化チタン
粒子を受けつつ重力によって下段に送り、下部からの空
気を通過させる多段の分散棚と、脱臭塔の内部に設けら
れ二酸化チタン粒子に吸着された悪臭ガス成分を光エネ
ルギで酸化分解して前記吸着性の再生を行うブラックラ
イトランプと、最下段の分散棚の二酸化チタン粒子を脱
臭塔の下方から上方へ搬送する粒体搬送手段とを備えた
光触媒流動循環式脱臭装置が開示されている。Further, in Japanese Patent Application Laid-Open No. 10-314544, the air to be treated before deodorization is fed from the lower part, and the treated air after deodorization is supplied from the upper part to the deodorizing tower and is supplied to the inside from the upper part of the deodorizing tower. , Titanium dioxide particles for adsorbing a malodorous gas component in the air to be treated for deodorization, and provided in multiple stages above and below the inside of the deodorization tower, sending titanium dioxide particles from the upper part to the lower part by gravity and from the lower part , A multi-stage dispersion shelf that allows the passage of air, a black light lamp that is provided inside the deodorization tower to oxidize and decompose the malodorous gas components adsorbed by the titanium dioxide particles with light energy to regenerate the adsorptivity, and the bottom stage , A photocatalyst fluidized circulation type deodorizing device is provided, which is provided with a granular material conveying means for conveying the titanium dioxide particles on the dispersion shelf from below to above the deodorizing tower.
【０００７】当該脱臭装置によれば、二酸化チタン粒子
用の再生塔を別途準備したり、脱臭塔と再生塔との間を
接続する２種の粒体搬送装置を設けることは回避される
ものの、それ以外の前記した問題点はそのまま残されて
いる。また、これらの脱臭装置では共通して、流動床を
構成するパンチングメタル、金網等による照射効率の低
下およびその摩耗によるダストの発生という問題が生じ
る虞がある。According to the deodorizing apparatus, although it is avoided to separately prepare a regenerating tower for titanium dioxide particles or to provide two kinds of granular material conveying devices for connecting the deodorizing tower and the regenerating tower, The other problems mentioned above are left as they are. Further, in common with these deodorizing devices, there is a possibility that problems such as reduction of irradiation efficiency due to punching metal, wire mesh, etc. forming a fluidized bed and generation of dust due to abrasion thereof may occur.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、粒状光触媒
を用いた高効率の気体浄化方法および気体浄化装置を提
供することを目的とするものである。SUMMARY OF THE INVENTION It is an object of the present invention to provide a highly efficient gas purification method and a gas purification apparatus using a granular photocatalyst.
【０００９】[0009]
【課題を解決するための手段】本発明の気体浄化方法
は、粒状光触媒を混合した汚染ガスを流動反応器に導入
し、該汚染ガスに紫外線照射条件下汚染物質を分解し、
流動反応器から排出した処理済ガスを、円筒形に成形し
たプリーツ状硬質シートフィルターを内蔵する分離器に
導入し、処理済ガスをフィルターを通過させて系外に排
気すると共に、分離した粒状光触媒を前記汚染ガスとの
混合過程に戻すことにより、粒状光触媒を循環させるこ
とを特徴とするものである。前記粒状光触媒の平均粒子
径は５〜５００ｎｍであることが好ましい。前記汚染ガ
スは、前記流動反応器内を上向き旋回流で通過させるこ
とが好ましい。本発明の気体浄化装置は、前記流動反応
器の軸方向に紫外線照射用の高出力水銀灯が設置されて
なることを特徴とするものである。前記流動反応器の内
壁面はミラー加工されてなることが好ましい。本発明の
気体浄化装置は、前記分離器内に前記フィルターのクリ
ーニング手段を有し、該クリーニング手段が圧縮空気に
よる衝撃波を、前記フィルターを支持するフレームに対
して付与するものであることが好ましい。The gas purification method of the present invention comprises introducing a pollutant gas mixed with a granular photocatalyst into a flow reactor and decomposing the pollutant gas into a pollutant under ultraviolet irradiation conditions.
The treated gas discharged from the flow reactor is introduced into a separator that has a pleated hard sheet filter formed into a cylindrical shape, and the treated gas is passed through the filter and discharged to the outside of the system, and the separated photocatalyst is also separated. The granular photocatalyst is circulated by returning to the mixing process with the polluted gas. The average particle size of the granular photocatalyst is preferably 5 to 500 nm. The pollutant gas is preferably passed through the flow reactor in an upward swirling flow. The gas purification apparatus of the present invention is characterized in that a high-power mercury lamp for ultraviolet irradiation is installed in the axial direction of the flow reactor. The inner wall surface of the fluidized reactor is preferably mirror processed. The gas purifying apparatus of the present invention preferably has a cleaning means for the filter in the separator, and the cleaning means applies a shock wave by compressed air to a frame supporting the filter.
【００１０】[0010]
【発明の実施の形態】以下、図面を参照しながら、本発
明の好適な実施形態を説明する。図１は本発明に係る気
体浄化方法の原理を示すフロー図である。各種汚染ガス
には粒状光触媒が混合された後、流動反応器に導入され
て紫外線照射を受け、汚染物質は分解反応が促進され
る。流動反応器を出た処理済ガスは粒状光触媒と分離さ
れた後、系外に排気されるが、このガスは脱臭、滅菌
（殺菌）、清浄化等の処理が完了したガスである。前記
分離された粒状光触媒は、再度、汚染ガスとの混合過程
に戻すことにより、系内を循環させる。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a flow chart showing the principle of the gas purification method according to the present invention. After a granular photocatalyst is mixed with various pollutant gases, it is introduced into a fluidized reactor and irradiated with ultraviolet rays to accelerate decomposition reaction of pollutants. The treated gas that has left the fluidized reactor is separated from the granular photocatalyst and then exhausted to the outside of the system. This gas is a gas that has undergone treatments such as deodorization, sterilization (sterilization), and cleaning. The separated photocatalyst is circulated in the system by returning to the mixing process with the pollutant gas again.
【００１１】本発明において汚染ガスとは、各種の汚染
物質を含有する気体をいうが、特に、悪臭ガスを含むも
のである。汚染ガスとして、養鶏・養豚場からの発生ガ
ス、食品生ごみ処理機の飼・肥料化に伴う悪臭ガス、病
院・福祉施設内からの発生ガスや薬品臭含有ガス、動物
実験施設・ペットショップ・屠殺場の悪臭ガス、食品加
工場の発生ガス、接着・塗装・プラスチック成形・加工
に伴う悪臭ガス、汚水・下水処理場やトイレなどの悪臭
ガス、ＩＣ製造・メッキ・表面処理工場からの発生ガ
ス、廃棄物処理場の悪臭ガス、並びに、土壌汚染・ＶＯ
Ｃ脱気ガス、ＮＯ X ・ＳＯX 含有大気ガス、道路トンネ
ル排気ガスを例示することができる。なお、我が国にお
いて悪臭防止法およびその関連条例で定められた規制基
準値は、アンモニア：１〜５ｐｐｍ、メチルメルカプタ
ン：０．００２〜０．０１ｐｐｍ、硫化水素：０．０２
〜０．２ｐｐｍ、硫化メチル：０．０１〜０．２ｐｐ
ｍ、二酸化メチル：０．０００９〜０．１ｐｐｍ、トリ
メチルアミン：０．００５〜０．０７ｐｐｍ、アセトア
ルデヒド：０．０５〜０．５ｐｐｍ、スチレン：０．４
〜２ｐｐｍ、等となっているが、本発明方法によれば、
これらの基準値を全てクリアすることができる。In the present invention, pollutant gas means various kinds of pollution.
Refers to a gas that contains a substance, but in particular, it also contains a malodorous gas
Of. As pollutant gas, gas generated from poultry and pig farms
, Odorous gas and diseases associated with feeding and fertilizing food garbage processing machines
Gas generated from hospitals and welfare facilities, gas containing chemical odor, animals
Laboratory facilities, pet shops, slaughterhouse odor gas, food
Factory generated gas, adhesion / painting / plastic molding / processing
Offensive odor gas, offensive odor from sewage / sewage treatment plants, toilets, etc.
Gas, IC manufacturing, plating, surface treatment factory
Gas, odorous gas from waste treatment plants, and soil pollution and VO
C degassing gas, NO X・ SOXContained atmospheric gas, road tunnel
Exhaust gas can be exemplified. In addition, in Japan
And the regulatory standards stipulated by the Odor Control Law and its related regulations.
Standard value is ammonia: 1 to 5 ppm, methyl mercapta
0.002 to 0.01 ppm, hydrogen sulfide: 0.02
~ 0.2 ppm, methyl sulfide: 0.01-0.2 pp
m, methyl dioxide: 0.0009 to 0.1 ppm, tri
Methylamine: 0.005-0.07ppm, acetoa
Ludehide: 0.05-0.5 ppm, styrene: 0.4
However, according to the method of the present invention,
All of these reference values can be cleared.
【００１２】光触媒は、汚染物質を含んだガス流によっ
て搬送可能な粒状体であればよい。このような微粒子状
の光触媒は既に市販されており、平均粒径が５〜５００
ｎｍ、特に、５〜２００ｎｍの二酸化チタン系のものが
好適である。二酸化チタン系の粒状光触媒はそれ自体が
３００ｍ2 ／ｇの比表面積を有しており、二酸化チタン
を担持した前記平板状のフィルターと比べて１００倍以
上の有効接触面積を有することになる。即ち、汚染ガス
は流動反応器内で十分な滞留時間、粒状光触媒と接触す
るので、非常に高い接触効率を有する。The photocatalyst may be any particulate material that can be carried by a gas stream containing contaminants. Such fine particle-shaped photocatalyst is already on the market and has an average particle size of 5 to 500.
nm, especially 5 to 200 nm of titanium dioxide type is suitable. The titanium dioxide-based granular photocatalyst itself has a specific surface area of 300 m 2 / g, and has an effective contact area of 100 times or more as compared with the flat plate-shaped filter supporting titanium dioxide. That is, since the polluted gas contacts the granular photocatalyst for a sufficient residence time in the fluidized reactor, it has a very high contact efficiency.
【００１３】流動反応器は、光触媒との接触時間と紫外
線照射時間が十分に取れる構造とすることが必要であ
る。好ましい流動反応器については後述する。二酸化チ
タンを光触媒とする汚染物質の分解反応メカニズムは、
現在、次のように進むと考えられている。即ち、二酸化
チタンに一定波長の光が当ると、電子（ｅ- ）が励起さ
れ、正孔（ｈ+ ）が発生する。電子（ｅ- ）は酸素（Ｏ
2 ）をスーパーオキサイドイオン（Ｏ2 - ）に変え、正
孔（ｈ+ ）は水（Ｈ2 Ｏ）をヒドロキシルラジカル（・
ＯＨ）に変える。これらのスーパーオキサイドイオン
（Ｏ2 - ）とヒドロキシルラジカル（・ＯＨ）は、共に
非常に強い酸化力を有しているので、有機化合物や無機
ガスが二酸化チタンの表面に接触すると、Ｃ−Ｏ結合や
Ｃ−Ｈ結合を切断し、中間生成物を経て有機化合物など
を最終的に二酸化炭素と水に分解する。なお、二酸化チ
タンには、結晶構造の相違から、ルチル、アナターゼ、
ブルッカイトがあり、光触媒としてはアナターゼ型が適
しているとされている。アナターゼ型二酸化チタンのバ
ンドギャップは３．２ｅＶであり、これを波長に換算す
ると３８８ｎｍとなることから、其れより短波長、即
ち、紫外線領域の光を二酸化チタンが吸収して、光反応
が起こることになる。It is necessary that the fluidized reactor has a structure that allows sufficient contact time with the photocatalyst and ultraviolet irradiation time. A preferred flow reactor will be described later. The decomposition reaction mechanism of pollutants using titanium dioxide as a photocatalyst is
At present, it is thought that the following will proceed. That is, when titanium dioxide is irradiated with light having a constant wavelength, electrons (e − ) are excited and holes (h + ) are generated. Electronic (e -) is oxygen (O
2 ) is changed to a superoxide ion (O 2 − ), and holes (h + ) turn water (H 2 O) into a hydroxyl radical (.
OH). Since both of these superoxide ions (O 2 − ) and hydroxyl radicals (· OH) have a very strong oxidizing power, when an organic compound or an inorganic gas comes into contact with the surface of titanium dioxide, a C—O bond is generated. Or C—H bond is cleaved, and an organic compound or the like is finally decomposed into carbon dioxide and water via an intermediate product. Incidentally, titanium dioxide, due to the difference in crystal structure, rutile, anatase,
There are brookite, and anatase type is said to be suitable as a photocatalyst. The band gap of anatase type titanium dioxide is 3.2 eV, and when converted to a wavelength, it becomes 388 nm. Therefore, titanium dioxide absorbs light of a shorter wavelength, that is, in the ultraviolet region, and a photoreaction occurs. It will be.
【００１４】光触媒と処理済ガスとを分離するための分
離器については後述するように、分離した粒状光触媒を
そのまま汚染ガスとの混合過程に循環利用できる構造の
ものが好ましい。As described below, the separator for separating the photocatalyst and the treated gas preferably has a structure in which the separated granular photocatalyst can be recycled as it is in the mixing process with the polluted gas.
【００１５】図２は本発明に係る気体浄化装置の構造を
示しており、塔型の流動反応器１０と同じく塔型の分離
器２０を主な構成部とし、これらは塔底部と塔頂部にお
いて、夫々、導入管１１と排出管１２により結ばれてい
る。なお、分離器２０については、後述するようにクリ
ーニング手段２６と排気ファン２７を設置したことか
ら、排出管１２の接続部位は、中程やや頂部寄りとなっ
ている。流動反応器１０内では、塔底部から塔頂部に向
けて粉体を同伴したガス流が上昇するようになってお
り、導入管１１の取り付け角度を流動反応器１０の器壁
接線方向とすることにより、上向き旋回流とすることが
好ましい。また、流動反応器１０の内壁面１６はミラー
加工を施し、次述する高出力水銀灯（ランプ）１５の照
射光を反射、再反射させるようにすることが好ましい。
流動反応器１０の容量については、ガス流量、粉体の流
量とその滞留時間などを考慮して決定するが、高出力水
銀灯１５以外の構造物は設けられておらず、空洞で、極
めて簡易な構造とすることが可能である。FIG. 2 shows the structure of the gas purifying apparatus according to the present invention. The tower type flow reactor 10 and the tower type separator 20 are the main components, and these are at the bottom and the top of the tower. , Are connected by an introduction pipe 11 and a discharge pipe 12, respectively. Regarding the separator 20, since the cleaning means 26 and the exhaust fan 27 are installed as will be described later, the connecting portion of the discharge pipe 12 is slightly closer to the top. In the fluidized reactor 10, the gas flow accompanied by the powder rises from the bottom of the tower toward the top of the tower, and the installation angle of the introduction pipe 11 should be the tangential direction of the vessel wall of the fluidized reactor 10. Therefore, the upward swirling flow is preferable. In addition, it is preferable that the inner wall surface 16 of the flow reactor 10 is mirror-processed so that the irradiation light of the high-power mercury lamp (lamp) 15 described below is reflected and re-reflected.
The capacity of the flow reactor 10 is determined in consideration of the gas flow rate, the powder flow rate and the residence time thereof, etc., but no structure other than the high-power mercury lamp 15 is provided, and the volume is very simple. It can be a structure.
【００１６】流動反応器１０の軸方向には高出力水銀灯
（ランプ）１５が設置されている。このため、粉体を同
伴したガスは高出力水銀灯１５を囲むようにして上昇
し、粉体は浮遊状態で流動するから、高出力水銀灯１５
による紫外線照射効率も非常に高くなる。高出力水銀灯
としては、低圧水銀灯以外の中圧水銀灯および高圧水銀
灯が含まれる。中圧水銀灯は１本で数ｋＷの出力があ
り、また、低圧水銀灯と比較すると、二酸化チタン系の
光触媒を活性化させるために必要な波長３８０ｎｍ以下
の紫外線を効率的に発生する。また、高出力水銀灯は低
圧水銀灯と比べて耐熱性が高く、高温ガスに対する装置
運転上の制約から開放される。A high power mercury lamp (lamp) 15 is installed in the axial direction of the flow reactor 10. Therefore, the gas entrained with the powder rises so as to surround the high-power mercury lamp 15, and the powder flows in a floating state.
The efficiency of UV irradiation is also very high. High-power mercury lamps include medium-pressure mercury lamps and high-pressure mercury lamps other than low-pressure mercury lamps. One medium-pressure mercury lamp has an output of several kW, and when compared with a low-pressure mercury lamp, it efficiently generates ultraviolet rays having a wavelength of 380 nm or less necessary for activating a titanium dioxide-based photocatalyst. In addition, the high-power mercury lamp has higher heat resistance than the low-pressure mercury lamp, and is free from the restrictions on the operation of the device against high-temperature gas.
【００１７】分離器２０の底部はホッパー２１とし、ホ
ッパー２１の下部は定量供給バルブ（ロータリーバル
ブ）２２を介して、導入管１１と接続されている。ま
た、ホッパー２１の上方であって、分離器２０の中央部
にはフィルター２５を設置し、排出管１２から分離器２
０内に流入してくるガスから光触媒を分離し、光触媒は
ホッパー２１へ降下させ、ガスはフィルター２５を通過
させて、頂部排気口２４から系外へ排気する。The bottom of the separator 20 is a hopper 21, and the lower part of the hopper 21 is connected to the introduction pipe 11 via a constant quantity supply valve (rotary valve) 22. Further, a filter 25 is installed above the hopper 21 and in the center of the separator 20, so that the filter 25 is connected to the separator 2 from the discharge pipe 12.
The photocatalyst is separated from the gas flowing into 0, the photocatalyst is lowered to the hopper 21, the gas passes through the filter 25, and is exhausted from the top exhaust port 24 to the outside of the system.
【００１８】フィルター２５の構造としては、簡易な構
造で、光触媒やガスに同伴されるダスト、ミストによる
目詰まりを生じないようにすることが重要である。本実
施形態では、円筒形に成形された硬質シートフィルター
を採用した。シートフィルターは、ポリエステル不織
布、セラミック、発泡プラスチック、発泡金属などの硬
質材料で構成すると共に、フィルター面積を大きく取る
ためにプリーツ状にシートを折り畳んで成形したものが
好ましい。前記のように本発明方法で使用する好適な光
触媒は、平均粒径が５〜５００ｎｍの範囲の微粉体であ
り、これらは通常のシートフィルターを通過してしまう
けれども、前記プリーツフィルターの場合、フィルター
表面に一定量の微粉体が付着して、また、微粉体同士が
集合して大きな塊状となることにより、所定のフィルタ
ー精度が得られるものである。塊状光触媒の粒径は０．
５〜３μｍ程度のものとなっている。It is important for the structure of the filter 25 to have a simple structure so as not to cause clogging due to dust and mist entrained in the photocatalyst or gas. In this embodiment, a hard sheet filter formed in a cylindrical shape is adopted. The sheet filter is preferably made of a hard material such as polyester non-woven fabric, ceramics, foamed plastic, or foamed metal, and is preferably formed by folding the sheet into pleats in order to secure a large filter area. As described above, the preferred photocatalyst used in the method of the present invention is a fine powder having an average particle size in the range of 5 to 500 nm, and although these pass through a normal sheet filter, in the case of the pleated filter, the filter is used. A certain amount of fine powder adheres to the surface, and the fine powders aggregate to form a large lump, so that a predetermined filter accuracy can be obtained. The particle size of the block photocatalyst is 0.
It is about 5 to 3 μm.
【００１９】分離器２０のシェル内においてフィルター
２５の上方には、フィルター２５のクリーニング手段２
６と排気ファン２７が設けられている。排気ファン２７
は分離器２０内の浄化済ガスの系外への排気を補助する
ためのものである。Above the filter 25 in the shell of the separator 20, a cleaning means 2 for the filter 25 is provided.
6 and an exhaust fan 27 are provided. Exhaust fan 27
Is for assisting the exhaust of the purified gas in the separator 20 to the outside of the system.
【００２０】前記プリーツフィルターは大きなフィルタ
ー面積を取ることができるものの、運転時間の経過に伴
い、粒状光触媒や粉塵の付着量が増大し微粒子による目
詰まりを起こし易くなる。そこで、本浄化装置を円滑に
操業するためには、自動的なクリーニング手段２６が不
可欠である。この種のクリーニング手段としては、ノッ
カーによるもの、または、噴出ノズルからプリーツフィ
ルター内部に向けたエアパルス噴射による振動付与方法
を採用することができる。さらに、本発明者による先願
発明である特開平１０−２３０１２１号公報記載の方法
が推奨される。当該方法は、大口径ノズルからプリーツ
フィルターを支持するフレームに向けて瞬間的に大量の
圧縮エアを放出することにより、フィルターに大きな衝
撃波を付与して、フィルターの外表面に付着した粉体を
完全に剥離するものである。Although the pleated filter can have a large filter area, the adhering amount of the granular photocatalyst or dust increases with the passage of operating time, and clogging with fine particles easily occurs. Therefore, the automatic cleaning means 26 is indispensable for the smooth operation of the present purifier. As this type of cleaning means, a knocker or a vibration applying method by air pulse injection from the ejection nozzle toward the inside of the pleated filter can be adopted. Furthermore, the method described in Japanese Patent Application Laid-Open No. 10-230121, which is a prior invention of the present inventor, is recommended. In this method, a large shock wave is applied to the filter by instantaneously discharging a large amount of compressed air from the large diameter nozzle toward the frame supporting the pleated filter, and the powder adhering to the outer surface of the filter is completely removed. It is to be peeled off.
【００２１】[0021]
【実施例】前記図２で説明した気体浄化装置を用いて、
アンモニアとＮＯ2 を含む模擬ガスによる実験を行っ
た。流動反応器１０は塔径３００ｍｍ、塔高１５００ｍ
ｍであり、内部には４ｋＷの高出力水銀灯１５が設けら
れている。粒状光触媒として、石原産業（株）製のＳＴ
−０１（平均粒径７ｎｍ）約５００ｇを用い、装置内で
循環使用した。また、分離器２０内には、ポリエステル
基材にＰＴＦＥ多孔質膜をラミネートしたプリーツフィ
ルター２５を設置した。このプリーツフィルターの精度
は、０．３μｍで９９．９５％以上である。導入管１１
からアンモニア１２ｐｐｍを含む模擬ガスを流速１ｍ／
秒で流し、排気口２４からの出口ガス中のアンモニア濃
度を測定したところ、４．５ｐｐｍであった。また、Ｎ
Ｏ2 １６ｐｐｍを含む模擬ガスを流速０．８ｍ／秒で流
し、排気口２４からの出口ガス中のＮＯ2 濃度を測定し
たところ、３ｐｐｍであった。本気体浄化装置により２
００日間の安定した連続運転を行った。EXAMPLE Using the gas purifying apparatus described in FIG.
An experiment was conducted using a simulated gas containing ammonia and NO 2 . The fluidized reactor 10 has a tower diameter of 300 mm and a tower height of 1500 m.
m, and a high-power mercury lamp 15 of 4 kW is provided inside. ST manufactured by Ishihara Sangyo Co., Ltd. as a granular photocatalyst
About 500 g of -01 (average particle size 7 nm) was used and circulated in the apparatus. Further, in the separator 20, a pleated filter 25 in which a PTFE porous film was laminated on a polyester substrate was installed. The accuracy of this pleated filter is 99.95% or more at 0.3 μm. Introductory pipe 11
From a simulated gas containing 12 ppm of ammonia at a flow rate of 1 m /
It was flowed for 2 seconds and the ammonia concentration in the outlet gas from the exhaust port 24 was measured and found to be 4.5 ppm. Also, N
A simulated gas containing 16 ppm of O 2 was flown at a flow rate of 0.8 m / sec, and the NO 2 concentration in the outlet gas from the exhaust port 24 was measured and found to be 3 ppm. 2 by this gas purification device
A stable continuous operation for 00 days was performed.
【００２２】[0022]
【発明の効果】本発明に係る気体浄化方法と装置によれ
ば、微粒子状の光触媒を用いているので浄化効率が極め
て高い。また、高温ガスに対しても適用できるので、生
ゴミ処理による発生ガスの脱臭、焼肉等のフードサービ
ス業に由来する発生ガスの脱臭、土壌汚染ＶＯＣガスの
浄化などの分野に適用することができる。さらに、構造
が極めて簡易であり、メンテナンス作業も容易であるこ
とから、安定した連続運転が可能である。According to the method and apparatus for purifying gas of the present invention, since the photocatalyst in the form of fine particles is used, the purification efficiency is extremely high. Further, since it can be applied to high temperature gas, it can be applied to fields such as deodorization of gas generated by garbage processing, deodorization of gas generated from food service industry such as grilled meat, and purification of soil-contaminated VOC gas. . Furthermore, since the structure is extremely simple and the maintenance work is easy, stable continuous operation is possible.
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明による気体浄化方法の原理を示すフロー
図である。FIG. 1 is a flow diagram showing the principle of a gas purification method according to the present invention.
【図２】本発明による気体浄化装置の構造を示す側面図
である。FIG. 2 is a side view showing the structure of the gas purifier according to the present invention.
１０ 流動反応器 １１ 導入管 １２ 排出管 １５ 高出力水銀灯 １６ 流動反応器内壁面 ２０ 分離器 ２１ ホッパー ２２ 定量供給バルブ ２５ フィルター ２６ クリーニング手段 ２７ 排気ファン 10 Flow reactor 11 Introduction tube 12 discharge pipe 15 High power mercury lamp 16 Flow reactor inner wall 20 separator 21 hopper 22 Constant supply valve 25 filters 26 Cleaning means 27 Exhaust fan
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4D002 AA02 AA03 AA06 AA13 AA14 AA32 AB02 AC10 BA04 BA09 BA14 CA09 DA11 DA21 EA07 GA01 GB12 4D048 AA06 AA08 AA22 BA07X BA41X BB17 CB03 CD05 CD08 EA01 4G069 AA02 AA15 BA04B BA48A CA17 DA08 EA01X EA01Y EB18X EB18Y EB19 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4D002 AA02 AA03 AA06 AA13 AA14 AA32 AB02 AC10 BA04 BA09 BA14 CA09 DA11 DA21 EA07 GA01 GB12 4D048 AA06 AA08 AA22 BA07X BA41X BB17 CB03 CD05 CD08 EA01 4G069 AA02 AA15 BA04B BA48A CA17 DA08 EA01X EA01Y EB18X EB18Y EB19
Claims (6)
応器に導入し、該汚染ガスに紫外線照射条件下汚染物質
を分解し、流動反応器から排出した処理済ガスを、円筒
形に成形したプリーツ状硬質シートフィルターを内蔵す
る分離器に導入し、処理済ガスをフィルターを通過させ
て系外に排気すると共に、分離した粒状光触媒を前記汚
染ガスとの混合過程に戻すことにより、粒状光触媒を循
環させることを特徴とする気体浄化方法。1. A pollutant gas mixed with a granular photocatalyst is introduced into a fluidized reactor, the pollutant is decomposed into the polluted gas under ultraviolet irradiation, and the treated gas discharged from the fluidized reactor is formed into a cylindrical shape. Introduced into a separator containing a pleated hard sheet filter, the treated gas is passed through the filter and exhausted to the outside of the system, and the separated granular photocatalyst is returned to the mixing process with the contaminated gas, thereby removing the granular photocatalyst. A gas purification method characterized by circulating.
０ｎｍである請求項１記載の気体浄化方法。2. The average particle size of the granular photocatalyst is 5 to 50.
The gas purifying method according to claim 1, wherein the gas purifying method is 0 nm.
き旋回流で通過する請求項１または請求項２記載の気体
浄化方法。3. The method for purifying gas according to claim 1, wherein the polluted gas passes through the flow reactor in an upward swirling flow.
体浄化方法に用いる気体浄化装置であって、前記流動反
応器の軸方向に紫外線照射用の高出力水銀灯が設置され
てなることを特徴とする気体浄化装置。4. A gas purifying apparatus for use in the gas purifying method according to claim 1, wherein a high-power mercury lamp for ultraviolet irradiation is installed in the axial direction of the flow reactor. A gas purifier characterized by.
れてなる請求項４記載の気体浄化装置。5. The gas purifying apparatus according to claim 4, wherein an inner wall surface of the flow reactor is mirror processed.
体浄化方法に用いる気体浄化装置であって、前記分離器
内に前記フィルターのクリーニング手段を有し、該クリ
ーニング手段が圧縮空気による衝撃波を、前記フィルタ
ーを支持するフレームに対して付与するものであること
を特徴とする気体浄化装置。6. A gas purifying apparatus for use in the gas purifying method according to claim 1, further comprising a cleaning means for the filter in the separator, wherein the cleaning means uses compressed air. A gas purifying device, characterized in that a shock wave is applied to a frame supporting the filter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002144716A JP2003334424A (en) | 2002-05-20 | 2002-05-20 | Gas cleaning method and apparatus therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002144716A JP2003334424A (en) | 2002-05-20 | 2002-05-20 | Gas cleaning method and apparatus therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003334424A true JP2003334424A (en) | 2003-11-25 |
Family
ID=29704310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002144716A Pending JP2003334424A (en) | 2002-05-20 | 2002-05-20 | Gas cleaning method and apparatus therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003334424A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008183217A (en) * | 2007-01-30 | 2008-08-14 | Utsunomiya Univ | Sterilizer |
| US7547418B2 (en) * | 2004-01-23 | 2009-06-16 | Gm Global Technology Operations, Inc. | Fluidized-bed reactor system |
| CN107029553A (en) * | 2017-06-21 | 2017-08-11 | 中山市科慧物联网科技有限公司 | A kind of high-level cleaner |
-
2002
- 2002-05-20 JP JP2002144716A patent/JP2003334424A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7547418B2 (en) * | 2004-01-23 | 2009-06-16 | Gm Global Technology Operations, Inc. | Fluidized-bed reactor system |
| JP2008183217A (en) * | 2007-01-30 | 2008-08-14 | Utsunomiya Univ | Sterilizer |
| CN107029553A (en) * | 2017-06-21 | 2017-08-11 | 中山市科慧物联网科技有限公司 | A kind of high-level cleaner |
| CN107029553B (en) * | 2017-06-21 | 2023-12-22 | 安徽灵杰环境净化科技有限公司 | High-efficient purifier |
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