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JP5274282B2 - Gas-liquid reaction method and gas-liquid reaction apparatus using microbubbles - Google Patents
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JP5274282B2 - Gas-liquid reaction method and gas-liquid reaction apparatus using microbubbles - Google Patents

Gas-liquid reaction method and gas-liquid reaction apparatus using microbubbles Download PDF

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JP5274282B2
JP5274282B2 JP2009019366A JP2009019366A JP5274282B2 JP 5274282 B2 JP5274282 B2 JP 5274282B2 JP 2009019366 A JP2009019366 A JP 2009019366A JP 2009019366 A JP2009019366 A JP 2009019366A JP 5274282 B2 JP5274282 B2 JP 5274282B2
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JP2010172842A (en
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芳行 坂東
泰人 川瀬
啓司 安田
友潔 竹山
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Nippon Refine Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas-liquid reaction method and apparatus which can improve ozone use efficiency from a standpoint of equipment engineering paying attention to a flow behavior of ozone microbubbles in an air-lift type gas-liquid reaction apparatus by installing a particular draft tube or partition plate in the apparatus. <P>SOLUTION: In the gas-liquid reaction method and apparatus, a microbubble generator is incorporated in an air-lift bubble column, a ratio of the cross section of a downflow portion to the column is controlled by a diameter of the draft tube and a position of the partition plate to control the flow behavior of the microbubbles in the column. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

本発明は、マイクロバブルを用いた有機物質を含有する排水等の気液反応処理方法及び処理装置に関する。   The present invention relates to a gas-liquid reaction treatment method and treatment apparatus for waste water and the like containing organic substances using microbubbles.

従来の難分解性有機物質を含む排水処理に当たっては、オゾン、紫外線、過酸化水素、フェントン試薬などやこれらを組み合わせた酸化促進法が実用化されているが、それらの方法は、通常の排水処理に較べていずれも運転のための経費が高くなるという欠点がある。従って、これらの酸化剤を効率的に機能させる操作方法の開発が強く望まれている。   In conventional wastewater treatment containing persistent organic substances, ozone, ultraviolet rays, hydrogen peroxide, Fenton reagent, etc., and oxidation promotion methods combining these have been put to practical use. Compared to the above, there is a drawback that the cost for operation becomes high. Therefore, there is a strong demand for the development of an operation method that allows these oxidizing agents to function efficiently.

最近、非特許文献1及び2に紹介されているように、気体の液中への溶解効率を改善するための気泡微細化技術としてマイクロバブル発生器が脚光を浴びており、種々の分野で実用されている。そして、特許文献1〜4および非特許文献3〜6においては、オゾンのマイクロバブル利用についても種々検討が行われており、更に、特許文献5〜7および非特許文献7では、曝気装置において、ドラフトチューブを設置することによって酸素の溶解効率を高める研究も行われている。しかしながら、オゾンを効率的に使用するためには、反応装置内でのオゾンマイクロバブルの流動挙動に着目した装置工学の観点からの改良が重要となる。   Recently, as introduced in Non-Patent Documents 1 and 2, a microbubble generator has been spotlighted as a bubble miniaturization technique for improving the dissolution efficiency of gas in liquid, and is practically used in various fields. Has been. In Patent Documents 1 to 4 and Non-Patent Documents 3 to 6, various studies have been made on the use of ozone microbubbles. Further, in Patent Documents 5 to 7 and Non-Patent Document 7, Research has also been conducted to increase the dissolution efficiency of oxygen by installing a draft tube. However, in order to use ozone efficiently, improvement from the viewpoint of apparatus engineering that focuses on the flow behavior of ozone microbubbles in the reaction apparatus is important.

特開2003−094076号公報JP 2003-094076 A 特開2004−321959号公報JP 2004-321959 A 特開2008−018378号公報JP 2008-018378 A 特開2008−055352号公報JP 2008-053552 A 特開平5−237488号公報JP-A-5-237488 特開2003−053371号公報JP 2003-053371 A 特開2006−110543号公報JP 2006-110543 A

大成博文、高橋正好ら:混相流、16,130−137(2002)Hirofumi Taisei, Masayoshi Takahashi et al .: Multiphase flow, 16, 130-137 (2002) 高橋正好:混相流、18,324−331(2004)Masayoshi Takahashi: Multiphase flow, 18,324-331 (2004) P.Li and H.Tsuge:J.Chem.Eng.Japan,39,1213−1220(2006)P. Li and H.H. Tsuge: J.M. Chem. Eng. Japan, 39, 1213-1220 (2006) M.Takahashi,K.Chiba and P.Li:J.Phys.Chem.B.,111,11443−11446(2007)M.M. Takahashi, K .; Chiba and P.M. Li: J. Phys. Chem. B. 111, 11443-11446 (2007) Y.Bando,T.Yoshimatsu,W.Luo,Y.Wang,K.Yasuda,M.Nakamura,Y.Funato and M.Oshima:J.Chem.Eng.Japan,41,562−567(2008)Y. Bando, T .; Yoshimatsu, W .; Luo, Y .; Wang, K .; Yasuda, M .; Nakamura, Y .; Funato and M.M. Oshima: J. Org. Chem. Eng. Japan, 41, 562-567 (2008) 坂東芳行、吉松崇、王宇飛、安田啓司、杉江享、浅井健好:日本混相流学会誌、混相流研究の進展3,51−57(2008)Yoshiyuki Bando, Takashi Yoshimatsu, Takashi Wang, Keiji Yasuda, Takashi Sugie, Takeyoshi Asai: Journal of the Japanese Society for Multiphase Flow, Progress in Multiphase Flow Research 3, 51-57 (2008) 王宇飛、深谷健也、吉松崇、安田啓司、坂東芳行、川瀬泰人:化学工学会第73年会、A309,浜松(2008)Wang Ufei, Kenya Fukaya, Takashi Yoshimatsu, Keiji Yasuda, Yoshiyuki Bando, Yasuto Kawase: Chemical Society of Japan 73rd Annual Meeting, A309, Hamamatsu (2008)

本発明はエアリフト式気液反応装置においてドラフトチューブまたは仕切り板を設置することによって、装置内でのオゾンマイクロバブルの流動挙動に着目した装置工学の観点からオゾンの利用効率を高め、かつエアリフト気泡塔へ流入する排水中の被分解物質濃度に応じてオゾン濃度を変化させると共に、ガス流量および液循環流量を一定に保つことができる気液反応方法および気液反応装置の提供を目的とする。 The present invention relates to an air lift type gas-liquid reaction apparatus, and by installing a draft tube or a partition plate, the use efficiency of ozone is enhanced from the viewpoint of apparatus engineering focusing on the flow behavior of ozone microbubbles in the apparatus , and the air lift An object of the present invention is to provide a gas-liquid reaction method and a gas-liquid reaction apparatus capable of changing the ozone concentration according to the concentration of decomposable substances in the waste water flowing into the bubble column and keeping the gas flow rate and the liquid circulation flow rate constant. .

本発明の第1は、ドラフトチューブまたは仕切り板を設置したエアリフト気泡塔にマイクロバブル発生器を組み込み、ドラフトチューブの径または仕切り板の位置によってエアリフト気泡塔に対する下降流部の断面積の割合を調整することにより、エアリフト気泡塔内におけるマイクロバブルの流動状態を制御し、かつエアリフト気泡塔へ流入する排水中の被分解物質濃度に応じてオゾン濃度を変化させると共に、ガス流量および液循環流量を一定に保つことを特徴とする、気液反応方法に関する。
本発明の第2は、前記エアリフト気泡塔において、塔に対する下降流部の断面積の割合が0.7以下のものである、請求項1記載の気液反応方法に関する。
本発明の第3は、前記マイクロバブル発生器に通される気体がオゾンである、請求項1または2記載の気液反応方法に関する。
本発明の第4は、エアリフト気泡塔内にドラフトチューブまたは仕切り板が設置され、塔底部にマイクロバブル発生器が組み込まれた気液反応装置であって、ドラフトチューブの径または仕切り板の位置によりエアリフト気泡塔に対する下降流部の断面積の割合を調整して塔内におけるマイクロバブルの流動状態を制御することができ、かつエアリフト気泡塔へ流入する排水中の被分解物質濃度に応じてオゾン濃度を変化させることができると共に、ガス流量および液循環流量を一定に保つことができるように設定されていることを特徴とする気液反応装置に関する。
本発明の第5は、前記エアリフト気泡塔において、塔に対する下降流部の断面積の割合が0.7以下である、請求項4記載の気液反応装置に関する。
本発明の第6は、前記マイクロバブル発生器に通される気体がオゾンである、請求項4または5記載の気液反応装置に関する。
The first aspect of the present invention incorporates a microbubble generator into an airlift bubble column equipped with a draft tube or partition plate, and adjusts the ratio of the cross-sectional area of the downflow section with respect to the airlift bubble column according to the diameter of the draft tube or the position of the partition plate by, by controlling the flow state of the micro-bubble in the air-lift bubble tower, and with varying the ozone concentration in response to the degradation substance concentration in the wastewater flowing into the air-lift bubble column, the gas flow rate and liquid circulation flow rate constant The present invention relates to a gas-liquid reaction method characterized in that the gas-liquid reaction is maintained .
2nd of this invention is related with the gas-liquid reaction method of Claim 1 whose ratio of the cross-sectional area of the downward flow part with respect to a tower is 0.7 or less in the said air lift bubble tower.
3rd of this invention is related with the gas-liquid reaction method of Claim 1 or 2 whose gas passed by the said microbubble generator is ozone.
The fourth of the present invention, the draft tube or the partition plate is installed in airlift bubble tower, a gas-liquid reactor microbubble generator is incorporated into the bottoms, the position of the diameter or the partition plate of the draft tube Can control the flow state of the microbubbles in the tower by adjusting the ratio of the cross-sectional area of the downflow section with respect to the airlift bubble column, and ozone according to the concentration of decomposable substances in the wastewater flowing into the airlift bubble column it is possible to change the concentration, to gas-liquid reactor you characterized in that it is configured to be able to maintain the gas flow rate and the liquid circulation flow rate constant.
5th of this invention is related with the gas-liquid reaction apparatus of Claim 4 whose ratio of the cross-sectional area of the downward flow part with respect to a tower is 0.7 or less in the said air lift bubble tower.
6th of this invention is related with the gas-liquid reaction apparatus of Claim 4 or 5 whose gas passed by the said microbubble generator is ozone.

本発明の気液反応方法及びその装置は、流量が一定で難分解性物質の濃度が経時的に大きく変化するような排水に対応して効果的な酸化処理方法となりうる。即ち、オゾンガスをマイクロバブル化することでオゾンの利用効率を高めると共に、ガス流量を一定とすることにより被分解物質濃度に応じてオゾン濃度を変化させることができるものである。   The gas-liquid reaction method and the apparatus of the present invention can be an effective oxidation treatment method corresponding to waste water in which the flow rate is constant and the concentration of the hardly decomposable substance changes greatly with time. That is, by making ozone gas into microbubbles, the ozone utilization efficiency can be improved, and the ozone concentration can be changed in accordance with the concentration of the substance to be decomposed by making the gas flow rate constant.

本発明で用いられるマイクロバブル化される気体には、空気、オゾン、酸素またはそれらの混合物が用いられる。   Air, ozone, oxygen, or a mixture thereof is used for the gas to be microbubbled used in the present invention.

対象となる排水には、ダイオキシン類、環境ホルモン、多環芳香族炭化水素(PAHs)、ポリビニルアルコール(PVA)、微量有機溶剤含有排水、界面活性剤混入排水等であり、また本発明が対象とする難分解性有機物としては、有機水銀化合物、有機砒素化合物、トリクロロエチレン、テトラクロロエチレン、四塩化炭素、ジクロロメタン、1,2−ジクロロエタン、1,1,1−トリクロロエタン、1,1,2−トリクロロエタン、1,1−ジクロロエチレン、シス−1,2−ジクロロエチレン、1,3−ジクロロプロペン(農薬)、チウラム(農薬)、シマジン(農薬)、チオベンカルブ(ベンチオカーブ)(農薬)、ベンゼン、クロロホルム、トランス−1,2−ジクロロエチレン、1,2−ジクロロプロパン、p−ジクロロベンゼン、イソキサチオン、ダイアジノン、フェニトロチオン(MEP)、イソプロチオラン、オキシン銅(有機銅)、クロロタロニル(TPN)、プロピザミド、EPN、ジクロルボス(DDVP)、フェノブカルブ(BPMC)、イプロベンホス(IBP)、クロルニトロフェン(CNP)、トルエン、キシレン、フタル酸ジエチルヘキシル、フェノール類、有機リン、陰イオン界面活性剤、非イオン界面活性剤、フタル酸エステル類、ヘキサクロロシクロヘキサン(HCH)、2−メチルイソボルネオール、ジオスミン、ホルムアルデヒド、ジクロロ酢酸、トリクロロ酢酸、ジクロロアセトニトリル、抱水クロラール、腐植質(フミン質)、1,4−ジオキサン、ダイオキシン類、ポリ塩化ビフェニル類、ポリ臭化ビフェニル類、ヘキサクロロベンゼン、ペンタクロロフェノール、2,4,5−トリクロロフェノキシ酢酸、2,4−ジクロロフェノキシ酢酸、アミトロール、アトラジン、アラクロール、シマジン、ヘキサクロロシクロヘキサン(HCH)、カルバリル、クロルデン、オキシクロルデン、トランス−ノナクロル、1,2−ジブロモ−3−クロロプロパン(DBCP)、DDT、DDE及びDDD、ケルセン(ジコホル)、アルドリン、エンドリン、ディルドリン、エンドスルファン(ベンゾエピン)、ヘプタクロル、ヘプタクロルエポキサイド、マラチオン(マラソン)、メソミル(ランネート)、メトキシクロル、マイレックス、ニトロフェン、トキサフェン(カンフェクロル)、トリブチルスズ(TBT)、トリフェニルスズ(TPT)、トリフルラリン、アルキルフェノール類、ビスフェノールA、フタル酸エステル類、フタル酸ジ−2−エチルヘキシル、フタル酸ブチルベンジン、フタル酸ジ−n−ブチル、フタル酸ジシクロヘキシル、フタル酸ジエチル、ベンゾ[a]ピレン、2,4−ジクロロフェノール、アジピン酸ジ−2−エチルヘキシル、ベンゾフェノン、4−ニトロトルエン、オクタクロロスチレン、アルディカーブ、ベノミル(ベンレート)、キーポン(クロルデコン)、マンゼブ(マンコゼブ)、マンネブ、メチラム、メトリブジン、シペルメトリン、エスフェンバレレート、フェンバレレート、ペルメトリン、ビンクロゾリン、ジネブ、ジラム、フタル酸ジペンチル、フタル酸ジヘキシル、フタル酸ジプロピルなどが挙げられる。   The target wastewater includes dioxins, environmental hormones, polycyclic aromatic hydrocarbons (PAHs), polyvinyl alcohol (PVA), wastewater containing a trace amount of organic solvent, wastewater mixed with a surfactant, etc. Examples of persistent organic substances include organic mercury compounds, organic arsenic compounds, trichloroethylene, tetrachloroethylene, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1, 1-dichloroethylene, cis-1,2-dichloroethylene, 1,3-dichloropropene (pesticide), thiuram (pesticide), simazine (pesticide), thiobencarb (bencho curve) (pesticide), benzene, chloroform, trans-1,2- Dichloroethylene, 1,2-dichloropropane, p-dichlorobenzene Zen, isoxathion, diazinon, fenitrothion (MEP), isoprothiolane, oxine copper (organic copper), chlorothalonil (TPN), propyzamide, EPN, dichlorvos (DDVP), fenocarb (BPMC), iprobenphos (IBP), chloronitrophen (CNP), toluene , Xylene, diethylhexyl phthalate, phenols, organic phosphorus, anionic surfactants, nonionic surfactants, phthalates, hexachlorocyclohexane (HCH), 2-methylisoborneol, diosmine, formaldehyde, dichloroacetic acid, Trichloroacetic acid, dichloroacetonitrile, chloral hydrate, humic substances (humic substances), 1,4-dioxane, dioxins, polychlorinated biphenyls, polybrominated biphenyls, hexa Lorobenzene, pentachlorophenol, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, amitrol, atrazine, alachlor, simazine, hexachlorocyclohexane (HCH), carbaryl, chlordane, oxychlordane, trans-nonachlor, 1,2-dibromo-3-chloropropane (DBCP), DDT, DDE and DDD, Kelsen (dicophol), aldrin, endrin, dieldrin, endosulfan (benzoepin), heptachlor, heptachlorepoxide, malathion (marathon), mesomil (lannate), Methoxychlor, Milex, Nitrophen, Toxaphene (Camphechlor), Tributyltin (TBT), Triphenyltin (TPT), Trifluralin, A Alkylphenols, bisphenol A, phthalates, di-2-ethylhexyl phthalate, butyl benzene phthalate, di-n-butyl phthalate, dicyclohexyl phthalate, diethyl phthalate, benzo [a] pyrene, 2,4 -Dichlorophenol, di-2-ethylhexyl adipate, benzophenone, 4-nitrotoluene, octachlorostyrene, aldicarb, benomyl (benlate), kepon (chlordecone), manzeb (mancozeb), manneb, methylam, metribidine, cypermethrin, es Examples include fenvalerate, fenvalerate, permethrin, vinclozolin, dineb, dilam, dipentyl phthalate, dihexyl phthalate, dipropyl phthalate, and the like.

図1で示されるのは、本発明の気液反応装置を用いた処理プロセス系の一例である。プロセス系全体は、調整槽Aと気液反応器Bから構成され、当該反応器にドラフトチューブあるいは仕切り板を設置したエアリフト気泡塔を用いる。調整槽では、気液反応器からの排オゾンガスと空気により排水が混合・攪拌される。調整槽のガス出口にはオゾン分解器Dを設置する。気液反応器はエアリフト気泡塔で、マイクロバブル発生器Cおよびその液循環系を有する。気液反応器へ流入する排水中の被分解物質濃度に応じてオゾン濃度を変化させる。なお、ガス流量および液循環流量は一定に保たれるので、気液反応器内の流動状態は不変となる。   FIG. 1 shows an example of a treatment process system using the gas-liquid reaction apparatus of the present invention. The entire process system is composed of a regulating tank A and a gas-liquid reactor B, and an air lift bubble column in which a draft tube or a partition plate is installed in the reactor is used. In the adjustment tank, the wastewater is mixed and stirred by the exhausted ozone gas and air from the gas-liquid reactor. An ozonolysis device D is installed at the gas outlet of the adjustment tank. The gas-liquid reactor is an airlift bubble column, and has a microbubble generator C and a liquid circulation system thereof. The ozone concentration is changed according to the concentration of the substance to be decomposed in the wastewater flowing into the gas-liquid reactor. Since the gas flow rate and the liquid circulation flow rate are kept constant, the flow state in the gas-liquid reactor remains unchanged.

気液反応器であるエアリフト気泡塔(ドラフトチューブを設置して、その内部に通気する場合)の概略を図2に示す。気泡塔(1)底部の下方にマイクロバブル発生器(3)を取り付ける。ドラフトチューブ(2)は当該気泡塔に対して同心円状に設置され、ドラフトチューブの内部にマイクロバブルが供給される。気液は塔底から上向並流として流され、塔頂の溢流管から排出されるように構成される。   FIG. 2 shows an outline of an air lift bubble column (when a draft tube is installed and vented to the inside) which is a gas-liquid reactor. A microbubble generator (3) is attached below the bottom of the bubble column (1). The draft tube (2) is installed concentrically with respect to the bubble column, and microbubbles are supplied into the draft tube. The gas and liquid flow from the bottom of the tower as a parallel upward flow, and are discharged from the overflow pipe at the top of the tower.

図2はドラフトチューブの内部に通気する場合であるが、通気方法やドラフトチューブ(2)に代えて仕切り板を設置することにより対応することも可能であり、その具体的な態様を図3で示している。即ち、ドラフトチューブの内部に通気する場合は図3a)となるが、同塔における塔とドラフトチューブとの環状部への通気〔図3b)〕や同塔内に仕切り板を設置する場合〔図3c)〕や矩形槽内に仕切り板を適用〔図3d)〕することも可能である。これらは、塔に対する下降流部分の断面積の割合とそこでの液速度に基づいて設計することができる。   FIG. 2 shows the case of venting the inside of the draft tube. However, it is possible to cope with this by installing a partition plate instead of the venting method or the draft tube (2). The specific mode is shown in FIG. Show. That is, FIG. 3a) shows the case of venting the inside of the draft tube, but the venting to the annular part of the tower and the draft tube in the tower [FIG. 3b)] and the case of installing the partition plate in the tower [FIG. 3c)] or a partition plate can be applied in the rectangular tank (FIG. 3d). These can be designed based on the ratio of the cross-sectional area of the downflow part to the column and the liquid velocity there.

本発明気液反応装置により、分解が困難な有機物質を含有しその濃度が経時的に変動する排水の処理を安価な運転経費で効率良く行うことができる。   According to the gas-liquid reactor of the present invention, wastewater containing an organic substance that is difficult to decompose and whose concentration fluctuates over time can be efficiently treated at a low operating cost.

気液反応装置を用いた処理プロセス(排水に対応する分解プロセス)を示す。A treatment process using a gas-liquid reactor (decomposition process corresponding to waste water) is shown. 気液反応装置の概略を示す。An outline of a gas-liquid reactor is shown. エアリフト気泡塔の構造を示す。The structure of an airlift bubble column is shown. 下降流部の液速度に及ぼす下降流部断面積の影響を示す。The influence of the cross-sectional area of the downflow part on the liquid velocity of the downflow part is shown. 下降流部の平均気泡径に及ぼす下降流部断面積の影響を示す。The influence of the cross-sectional area of the downflow part on the average bubble diameter of the downflow part is shown. 液相基準物質移動容量係数に及ぼす下降流部断面積の影響を示す。The influence of the downflow cross-sectional area on the liquid phase reference mass transfer capacity coefficient is shown. 分解率に及ぼす下降流部断面積の影響を示す。The influence of the downflow cross-sectional area on the decomposition rate is shown.

以下に実施例を挙げて本発明を説明するが、本発明はこれによって何らの限定を受けるものではない。
〔実施例〕
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
〔Example〕

気泡塔は内径0.190m、高さ1.90mの透明アクリル樹脂製とした。塔底部の下方にマイクロバブル発生器を取り付けた。塔頂からポンプへの液配管を設置し、液配管には液温度を一定とするための冷却器を取り付けた。ドラフトチューブは肉厚5mmの透明アクリル樹脂管で、塔に対して同心状に設置した。ドラフトチューブの長さは1.00mで一定とし、ドラフトチューブの径は0.070〜0.160mの範囲で変えた。塔断面積基準のガス空塔速度を0.29mm/s、液空塔速度を5mm/sで一定とした。なお、空塔速度とはガスまたは液の流量を塔断面積で除した値である。
流動特性の測定では、ガスに空気、液に水道水を用いた。流動状態を観察し、下降流部(塔とドラフトチューブとの間の環状部分)における液速度、下降流部における平均気泡径及び物質移動容量係数を測定した。平均気泡径は、硬性鏡と高速ビデオを組み合せて撮影したビデオ画像から求めた気泡径分布から算出した。
分解性能の測定では、ガスにオゾンガス、液にメチレンブルー(被分解物質)水溶液を用いた。オゾンガスの濃度は59g/m、メチレンブルーの濃度は3mmol/mとした。4分間オゾンを通気した後のメチレンブルー濃度を分析し、分解率を求めた。
The bubble column was made of a transparent acrylic resin having an inner diameter of 0.190 m and a height of 1.90 m. A microbubble generator was attached below the bottom of the tower. A liquid pipe from the top of the tower to the pump was installed, and a cooler for keeping the liquid temperature constant was attached to the liquid pipe. The draft tube was a transparent acrylic resin tube having a thickness of 5 mm, and was installed concentrically with the tower. The length of the draft tube was fixed at 1.00 m, and the diameter of the draft tube was changed in the range of 0.070 to 0.160 m. The gas superficial velocity based on the cross-sectional area of the tower was constant at 0.29 mm / s and the liquid superficial velocity was 5 mm / s. The superficial velocity is a value obtained by dividing the gas or liquid flow rate by the cross-sectional area of the tower.
In measuring the flow characteristics, air was used for the gas and tap water was used for the liquid. The flow state was observed, and the liquid velocity in the downward flow portion (annular portion between the tower and the draft tube), the average bubble diameter in the downward flow portion, and the mass transfer capacity coefficient were measured. The average bubble diameter was calculated from the bubble diameter distribution obtained from a video image taken by combining a rigid endoscope and a high-speed video.
In the measurement of decomposition performance, ozone gas was used as the gas and methylene blue (substance to be decomposed) aqueous solution was used as the liquid. The concentration of ozone gas was 59 g / m 3 , and the concentration of methylene blue was 3 mmol / m 3 . The concentration of methylene blue after aeration of ozone for 4 minutes was analyzed to determine the decomposition rate.

本実施例では、加圧ポンプと旋回流を利用するラインミキサから構成されるマイクロバブル発生器を用いたが、これに限定するものではなく、他のマイクロバブル発生法、例えばキャビテーション方式やフィルター方式などでも構わない。   In this embodiment, a microbubble generator composed of a pressure pump and a line mixer using a swirl flow is used, but the present invention is not limited to this, and other microbubble generation methods such as a cavitation method and a filter method are used. It doesn't matter.

通常のガス分散器(ノズルや多孔質分散器)を用いてミリサイズの気泡を分散させる場合、本測定範囲のガス速度では気泡は下降流部(塔とドラフトチューブとの間の環状部分)に同伴されない。マイクロバブルを分散させる場合、ドラフトチューブ上端付近においてドラフトチューブ内部を上昇する気泡群のうち大気泡はさらに上方へ流れて液面から排出し、多くのマイクロバブルは液循環流により下降流部へ同伴される。ガス速度が高くなるにつれて、液循環流量が高くなり、下降流部へのマイクロバブルの同伴量が増える。大きいドラフトチューブではマイクロバブルは下降流部を円滑に流下するが、小さいドラフトチューブではかなり乱れて流下する。   When dispersing millimeter-sized bubbles using a normal gas disperser (nozzle or porous disperser), the bubbles are in the downflow part (annular part between the tower and the draft tube) at the gas velocity in this measurement range. Not accompanied. When dispersing microbubbles, large bubbles of the bubbles that rise inside the draft tube near the upper end of the draft tube flow further upward and are discharged from the liquid surface. Is done. As the gas velocity increases, the liquid circulation flow rate increases and the amount of microbubbles accompanying the downward flow portion increases. In the large draft tube, the microbubbles smoothly flow down the downflow part, but in the small draft tube, the microbubbles flow considerably turbulently.

図4において、下降流部の液速度に及ぼす下降流部断面積の影響を示す。エアリフト気泡塔では非通気部が下降流部となる。横軸は、塔の断面積に対する下降流部の断面積の割合である。下降流部の液速度は、下降流部断面積の割合が小さくなるにつれて高くなる。   FIG. 4 shows the influence of the cross-sectional area of the downward flow portion on the liquid velocity of the downward flow portion. In the air lift bubble column, the non-venting portion becomes the downward flow portion. The horizontal axis represents the ratio of the cross-sectional area of the downflow portion to the cross-sectional area of the tower. The liquid velocity in the downward flow portion increases as the ratio of the cross-sectional area of the downward flow portion decreases.

図5には、下降流部の平均気泡径に及ぼす下降流部断面積の割合の影響を示す。平均気泡径は、下降流部断面積の割合が小さくなるにつれて増大する。これは、下降流部断面積の割合が小さくなるほど下降流部における液速度が高くなる(図4)ので、より大きなマイクロバブルも下降流部へ同伴されるためである。このことは、下降流部の液速度により下降流部へ同伴されるマイクロバブルの大きさを制御できることを意味する。   FIG. 5 shows the influence of the ratio of the cross-sectional area of the downflow portion on the average bubble diameter of the downflow portion. The average bubble diameter increases as the ratio of the cross-sectional area of the downward flow portion decreases. This is because the smaller the ratio of the cross-sectional area of the downward flow portion, the higher the liquid velocity in the downward flow portion (FIG. 4), so that larger microbubbles are also entrained in the downward flow portion. This means that the size of the microbubbles entrained in the downward flow portion can be controlled by the liquid velocity of the downward flow portion.

図6に、液相基準物質移動容量係数に及ぼす下降流部断面積の割合の影響を示す。横軸1.0の値はドラフトチューブのない場合のデータである。ドラフトチューブを設置することにより、物質移動容量係数は著しく高くなる。これは、下降流部に同伴されるマイクロバブルが物質移動を大きく促進するためである。また、下降流部断面積の割合が小さくなるにつれて、下降流部の断面積が小さくなるにもかかわらず物質移動容量係数は高くなり、下降流部断面積の割合が0.7以下になるとほぼ一定となる。なお、液相基準物質移動容量係数kaとは、気液系でガスが分散相となる(液中に気泡が分散する状況)気液接触装置における物質移動性能を表す値である(物質移動容量係数が高いほど、性能の高い装置となる)。kは液相基準物質移動係数、aは比界面積(装置の単位体積あたりの気液界面積)を意味するが,両者が高いほど物質移動性能は高くなる。装置工学では両者の積である液相基準物質移動容量係数で装置性能を比較する。 FIG. 6 shows the influence of the ratio of the cross-sectional area of the downflow portion on the liquid phase reference mass transfer capacity coefficient. The value of 1.0 on the horizontal axis is data when there is no draft tube. By installing a draft tube, the mass transfer capacity coefficient is significantly increased. This is because the microbubbles entrained in the downward flow part greatly accelerates the mass transfer. Further, as the ratio of the cross-sectional area of the downward flow portion becomes small, the mass transfer capacity coefficient increases despite the fact that the cross-sectional area of the downward flow portion becomes small. It becomes constant. The liquid phase reference mass transfer capacity coefficient k L a is a value that represents the mass transfer performance in the gas-liquid contact device in which the gas is in a dispersed phase in a gas-liquid system (the situation where bubbles are dispersed in the liquid) (substance The higher the moving capacity factor, the better the device.) k L is a liquid phase reference mass transfer coefficient, and a is a specific interface area (gas-liquid interface area per unit volume of the apparatus). The higher the both, the higher the mass transfer performance. In device engineering, device performance is compared with the liquid phase reference mass transfer capacity coefficient, which is the product of both.

図7に、分解率に及ぼす下降流部断面積の割合の影響を示す。上記図6と同様、横軸1.0の値はドラフトチューブのない場合のデータである。物質移動容量係数と同様、分解率は、下降流部断面積の割合が小さくなるにつれて高くなり、下降流部断面積の割合が0.7より小さくなるとほぼ一定となる。また、分解率が物質移動容量係数と同様な傾向を示すことより、オゾンの溶解効率を高めるには、気液物質移動が重要因子であることがわかる。   FIG. 7 shows the influence of the ratio of the downflow cross-sectional area on the decomposition rate. Similar to FIG. 6 above, the value on the horizontal axis 1.0 is data when there is no draft tube. Similar to the mass transfer capacity coefficient, the decomposition rate increases as the ratio of the cross-sectional area of the downflow portion decreases, and becomes substantially constant when the ratio of the cross-sectional area of the downflow portion becomes smaller than 0.7. Moreover, it can be seen that gas-liquid mass transfer is an important factor for improving the dissolution efficiency of ozone because the decomposition rate shows the same tendency as the mass transfer capacity coefficient.

図6および図7の結果より、オゾンの溶解効率を高めるには塔の断面積に対する下降流部の断面積の割合を0.7以下にすることが有効であることがわかる。なお、この下降流部断面積の割合が0.7以下になると液の循環流が極めて低くなり、またマイクロバブルの循環流も少なくなるため、分解性能は低下する。このことは、ドラフトチューブを設置した円塔の環状部に通気する場合、仕切り板を設置した円塔や矩形槽を用いる場合にも適用できる。   From the results of FIGS. 6 and 7, it can be seen that it is effective to reduce the ratio of the cross-sectional area of the downflow portion to the cross-sectional area of the tower to 0.7 or less in order to increase the ozone dissolution efficiency. When the ratio of the cross-sectional area of the downward flow portion is 0.7 or less, the liquid circulation flow becomes extremely low, and the microbubble circulation flow also decreases, so that the decomposition performance is lowered. This can also be applied to the case where a circular tower or a rectangular tank provided with a partition plate is used in the case of ventilating the annular part of the circular tower provided with the draft tube.

下降流部の断面積 [m
A 塔の断面積 [m
/A 塔断面積に対する下降流部の断面積の割合 [−]
L,D 下降流部における液速度 [mm/s]
AVE,D 下降流部における平均気泡径 [μm]
a 液相基準物質移動容量係数(aは比界面積) [1/s]
X 分解率 [−]
AD Cross-sectional area of downflow part [m 2 ]
A Sectional area of the tower [m 2 ]
A D / A Ratio of the cross-sectional area of the downflow portion to the cross-sectional area of the tower [−]
u Liquid velocity in the L, D downward flow [mm / s]
d AVE, D Average bubble diameter in the downflow part [μm]
k L a Liquid phase reference mass transfer capacity coefficient (a is specific interface area) [1 / s]
X Decomposition rate [-]

Claims (6)

ドラフトチューブまたは仕切り板を設置したエアリフト気泡塔にマイクロバブル発生器を組み込み、ドラフトチューブの径または仕切り板の位置によってエアリフト気泡塔に対する下降流部の断面積の割合を調整することにより、エアリフト気泡塔内におけるマイクロバブルの流動状態を制御し、かつエアリフト気泡塔へ流入する排水中の被分解物質濃度に応じてオゾン濃度を変化させると共に、ガス流量および液循環流量を一定に保つことを特徴とする、気液反応方法。 By incorporating a microbubble generator into an airlift bubble column with a draft tube or partition plate, and adjusting the ratio of the cross-sectional area of the downflow section with respect to the airlift bubble column according to the diameter of the draft tube or the position of the partition plate, It is characterized by controlling the flow state of microbubbles in the interior and changing the ozone concentration according to the concentration of the substance to be decomposed in the waste water flowing into the air lift bubble column, and keeping the gas flow rate and the liquid circulation flow rate constant. Gas-liquid reaction method. 前記エアリフト気泡塔において、塔に対する下降流部の断面積の割合が0.7以下のものである、請求項1記載の気液反応方法。   The gas-liquid reaction method according to claim 1, wherein in the air lift bubble column, the ratio of the cross-sectional area of the downward flow portion to the column is 0.7 or less. 前記マイクロバブル発生器に通される気体がオゾンである、請求項1または2記載の気液反応方法。 The gas-liquid reaction method according to claim 1 or 2, wherein the gas passed through the microbubble generator is ozone. エアリフト気泡塔内にドラフトチューブまたは仕切り板が設置され、塔底部にマイクロバブル発生器が組み込まれた気液反応装置であって、ドラフトチューブの径または仕切り板の位置によりエアリフト気泡塔に対する下降流部の断面積の割合を調整して塔内におけるマイクロバブルの流動状態を制御することができ、かつエアリフト気泡塔へ流入する排水中の被分解物質濃度に応じてオゾン濃度を変化させることができると共に、ガス流量および液循環流量を一定に保つことができるように設定されていることを特徴とする気液反応装置。 Draft tube or the partition plate is installed in airlift bubble tower, a gas-liquid reactor microbubble generator is incorporated into the bottoms downflow for airlift bubble column according to the position of the diameter or the partition plate of the draft tube The flow rate of microbubbles in the tower can be controlled by adjusting the ratio of the cross-sectional area of the section, and the ozone concentration can be changed according to the concentration of decomposed substances in the wastewater flowing into the airlift bubble tower with the gas-liquid reactor characterized in that it is configured to be able to maintain the gas flow rate and the liquid circulation flow rate constant. 前記エアリフト気泡塔において、塔に対する下降流部の断面積の割合が0.7以下である、請求項4記載の気液反応装置。The gas-liquid reactor according to claim 4, wherein in the air lift bubble column, the ratio of the cross-sectional area of the downward flow portion to the column is 0.7 or less. 前記マイクロバブル発生器に通される気体がオゾンである、請求項4または5記載の気液反応装置。The gas-liquid reaction apparatus according to claim 4 or 5, wherein the gas passed through the microbubble generator is ozone.
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