TWI226311B - Hydrogen peroxide containing water discharge treatment device - Google Patents

Hydrogen peroxide containing water discharge treatment device Download PDF

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Publication number
TWI226311B
TWI226311B TW091136694A TW91136694A TWI226311B TW I226311 B TWI226311 B TW I226311B TW 091136694 A TW091136694 A TW 091136694A TW 91136694 A TW91136694 A TW 91136694A TW I226311 B TWI226311 B TW I226311B
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Taiwan
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hydrogen peroxide
catalyst layer
catalyst
reaction tower
treatment device
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TW091136694A
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Chinese (zh)
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TW200301227A (en
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Kazuya Uesugi
Teruo Sugizaki
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Organo Corp
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Publication of TWI226311B publication Critical patent/TWI226311B/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24Stationary reactors without moving elements inside
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/70Treatment of water, waste water, or sewage by reduction
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/346Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from semiconductor processing, e.g. waste water from polishing of wafers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Catalysts (AREA)
  • Removal Of Specific Substances (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

The hydrogen peroxide containing water discharge treatment device disclosed in this invention is to allow the hydrogen peroxide containing discharge water flowing upwards in a reaction tower (2). Moreover, catalyst is in the reaction tower (2), which is divided in a top and bottom manner, into a two-layered arrangement of a bottom catalyst layer (8) and a top catalyst layer (14). In addition, there is an exhaust pipe (20) installed onto the reaction tower (2) so that the oxygen generated in the bottom catalyst layer can be discharged out of the reaction tower without contact the top catalyst layer. Therefore, contact efficiency of catalyst and hydrogen peroxide can be increased, the size of the device can be reduced, space can be saved and equipment cost can be reduced.

Description

1226311 玖、發明說明 【發明所屬之技術領域】 本發明係關於半導體製造排水、食品容器洗淨排水之類 的各種含有過氧化氫排水之處理裝置。 【先前技術】 過氧化氫具優越的洗淨效果、殺菌效果,而且因爲在反 應後將分解爲氧與水的淸洗藥品,因此廣泛的使用爲製造 步驟的洗淨劑、殺菌劑。譬如,在半導體裝置之製造工廠 中’於各種步驟中過氧化氫將被使用於晶圓洗淨等方面。 使用於洗淨、殺菌用的過氧化氫,將從製’造步驟中當作 廢液(含過氧化氫之排水)而被排放出。此廢液就從擁有殺 菌力、構成COD肇因物質等觀點而言,最好不要直接排放 於公用水域中。 習知含有過氧化氫排水之處理方法,雖採用亞硫酸鈉等 還原劑、或過氧化氫等酵素劑的處理,但是該等方法卻潛 在有藥物使用量較多,增加運轉成本等問題。 此外,已知有採用活性碳、錳載持觸媒、白金載持觸媒 等還原觸媒,而將過氧化氫予以還原的手法。排水中的過 氧化氫係藉由接觸上述還原觸媒,而分解爲氧與水。藉由 採用此種還原觸媒的處理手法,便可將含過氧化氫排水之 處理所需的運轉成本予以抑制降低。 採用還原觸媒的含有過氧化氫排水之處理,雖具有上述 優點,但是此處理在相較於採用還原劑、酵素劑之處理的 情況下,卻將潛在有處理設備將變得比較大的問題。 6 312/發明說明書(補件)/92-03/91136694 1226311 【發明內容】 (發明揭示) 本發明係提供一種採用可有效率執行處理之過氧化氫 分解觸媒(還原觸媒)的含有過氧化氫排水之處理裝置。 本發明係關於在塡充著過氧化氫分解觸媒的反應塔 內,將含過氧化氫之排水朝上流通進行通水,俾將過氧化 氫分解爲氧與氫的處理裝置。上述過氧化氫分解觸媒係在 反應塔內,朝上下方向分割爲複數層而配置著。然後,在 反應纟合內設置者至少將最下方觸媒層所產生的氧氣,在不 致接觸到較其更上方觸媒層的前提下排放出於反應塔外的 排氣管。 藉此,便可有效的執行過氧化氫之分解。 【實施方式】 (發明之較佳實施形態) 首先,爲求完成本發明,本發明便進行下述①〜④所述 的探討。 ① 利用觸媒的反應系統,一般乃藉由提昇觸媒與反應對 象物(在本發明中爲水中的過氧化氫)間之接觸效率,而提 高反應效率,結果便可使裝置小型化,並降低設備費。 ② 此外,採用還原觸媒的含有過氧化氫之排水處理裝 置,在塡充著觸媒的反應塔中,使含過氧化氫之排水朝上 流動或朝下流動而連續通水,而從反應塔上部或下部獲得 處理水者乃屬一般方式。其中,當將高濃度過氧化氫進行 分解處理之情況時,因爲將產生大量氧氣,且其將成爲氣 312/發明說明書(補件)/92-03/91136694 1226311 泡並引發封閉於塡充層內的現象,因此就從裝置構造的簡 單性、系統的安全性觀點而言,最好選擇較容易從反應塔 上部放出氣體的朝上流動方式。 ③ 但是,在過氧化氫分解時所產生的氧氣氣泡,可判斷 將降低觸媒與過氧化氫間的接觸效率,結果便將降低處理 裝置的反應效率。特別係當處理著含高濃度過氧化氫之排 水的情況時,依先前所述理由,雖最好採用朝上流動式反 應塔,但是所產生氧氣氣泡在觸媒層內進行上升的過程 中,推測氣泡將妨礙觸媒與排水間的接觸。 ④ 所以,本發明便針對防止所產生的氧氣氣泡,阻礙觸 媒與過氧化氫間之接觸的方法進行探討。結果,在利用使 含過氧化氫之排水朝上流動而進行處理的反應塔中,在反 應塔內將觸媒朝上下方向分割爲複數層而配置著,同時藉 由使在下方觸媒層所產生的氧氣氣泡不致接觸於上方觸媒 層的前提下,排放出於反應塔外,便可使上方觸媒層在不 致受到下方觸媒層所產生氧氣氣體氣泡的阻礙之情況下, 產生觸媒與過氧化氫的接觸,結果發現將提昇反應塔中的 過氧化氫去除率。.此外,此時藉由將氧氣氣體排放管設置 於反應塔內,發現可將在觸媒層所產生的氧氣氣體進行良 好的排出。 本實施形態的裝置係在塡充著過氧化氫分解觸媒的反 應塔內,使含過氧化氫之排水朝上流動而通水,俾將過氧 化氫分解爲氧與水的處理裝置。然後,在反應塔內設置著 至少將最下方觸媒層所產生的氧氣,在不致接觸到較其更 312/發明說明書(補件)/92-03/91136694 8 1226311 上方觸媒層的前提下排放出於反應塔外的排氣管° 此情況下,到底將過氧化氫分解觸媒分割爲多少層雖可 進行適當的決定,但是通常爲2層〜4層’特別以分割爲2 層爲恰當。 再者,本實施形態之處理裝置,因爲在最下方觸媒層所 產生的氧氣產生量最多,因而雖設置有至少將最下方觸媒 層所產生的氧氣排放出於反應塔外的排氣管’但是若將各 觸媒層中所產生的氣體分別各自排放出於反應塔外的排氣 管的話,將更爲恰當。 另外,利用排氣管而進行氧氣的排放,僅要可有效防止 所產生的氧氣氣泡,在上方觸媒層中阻礙到觸媒與過氧化 氫間之接觸程度而排放出的話便可。所以,未必需要將在 觸媒層中所產生的氣體全部排放出,亦可部分排放出。 在本實施形態中,過氧化氫分解觸媒的種類並無限定, 僅要可將過氧化氫予以還原並分解爲氧與水的話便可。過 氧化氫分解觸媒具體而言可舉例如:白金、鈀、錳等金屬觸 媒、或活性碳等。此外,亦可採用在由活性碳、氧化鋁、 氧化矽等所構成的母體上,載持著白金、鈀、錳等金屬類 的觸媒。 再者,在本實施形態中,朝上下方向被分割爲複數層而 配置之各觸媒層的觸媒塡充量,在考慮排水中的過氧化氫 濃度、排水通水速度、所設定的過氧化氫去除率等各種因 素之下’可進行任意設定。此外,在各觸媒層中亦可塡充 著種類不同的觸媒。 9 312/發明說明書(補件)/92-03/91136694 1226311 以下,針對本發明實施形態,根據圖示進行說明。 圖1所示係本發明含有過氧化氫之排水處理裝置一實施 形態槪略圖。在圖1中,反應塔2係形成如圓筒狀。原水 供應管4係依從外部插入於反應塔2底部之形態而固定 著。在反應塔2底部中設置有支撐砂礫層6,原水供應管4 便開口於此支撐砂礫層6內。在反應塔2內的支撐砂碟層 6上,依序形成下觸媒層8、上觸媒支撐板1 〇、支撐砂碟 層1 2、上觸媒層1 4。支撐砂礫層6,1 2係分別支撐著下觸 媒層8、上觸媒層1 4,乃由粒徑較大於構成下觸媒層8、 上觸媒層1 4之觸媒粒子的大粒徑支撐材所構成。 再者,在上觸媒層1 4上方設置著上端開放的L字型處 理水排放管1 6,並溢流排放反應塔2內的處理水(上呈淸 水)。此外,在反應塔2上端設置著將內部氣體予以排放出 的氣體排放口 1 8。然後,貫穿反應塔2之上觸媒支撐板1 0、 支撐砂礫層1 2、.及上觸媒層1 4而設置著排氣管2 0。此排 氣管2 0係下端由上觸媒支撐板1 〇支撐著,而上端則由配 置於反應塔2上端的排氣管支撐體22所支撐著。 其中,在支撐著支撐砂礫層12與上觸媒層14之上觸媒 支撐板1 0上,設置著如圖2所示的8個集水口(收集 網)24、及4個排氣口 26,各排氣口 26分別連接於排氣管 2 0下端。換句話說’在圖1中,雖僅圖示著一條排氣管2 〇, 但是排氣管20乃對應著各排氣口 26而設置,在本裝置中 設置著合計4條排氣管2 0。此外,該等排氣管2 〇係貫穿 上觸媒層1 4並在塔上端的處理水水面3 〇上方處開口著。 10 312/發明說明書(補件)/92-03/9113 6694 1226311 換句話說,排氣管2 0上端將到達處理水排放管1 6上端開 口更上方位置處。另外,上觸媒支撐板1 0係配置於下觸媒 層8上方,在下觸媒層8與上觸媒支撐板1 0之間將形成空 間部3 2。 如此的話,在本裝置中,便將觸媒層分爲上下2層(下觸 媒層8與上觸媒層1 4)並設置於反應塔2內,且設置有將 上觸媒層14旁路(bypass)用的排氣管20。 在此種裝置中,含過氧化氫之排水2 8將經由原水供應 管4而供應給反應塔2下端。在反應塔2下端設置著支撐 砂礫層6。含過氧化氫之排水係在支撐砂礫層6內,瀰漫 於反應塔2內部全區域中。 如上述,在反應塔2中段設置著上觸媒層1 4的支撐板 1 〇,而在此支撐板1 0下方形成空間部3 2,同時在此支撐 板1 〇上,如前述設置著供收集著由下觸媒層8所產生氧氣 用的排氣口 2 6。所以,排氣口 2 6便連接延伸至較反應塔2 上端之下觸媒層8更上方的排氣管2 0。所以,此排氣管2 0 便將下觸媒層8中所產生氧氣的其中一部份或全部,從支 撐板1 〇之排氣口 2 6經由排氣管2 0到達上觸媒層1 4上端, 且在不致接觸於上觸媒層1 4之觸媒的情況下,便被排放出 於系統外。 再者,反應塔中段的支撐板1 0上,設置著不同於排氣 口 2 6之供將排放水導向於上觸媒層1 4用的另設集水口 2 4。經去除部分或全部產生氣體的排放水,便將透過此集 水口 2 4而通水於上觸媒層1 4內,排放水中的過氧化氫便 11 312/發明說明書(補件)/92-03/91136694 1226311 將更被進行還原分解。通過上觸媒層1 4的排放水,將到達 塔上端的水面3 0,並經由處理水排放管1 6而排放出於反 應塔2外。通過排氣管20而被導向於水面上端之來自下觸 媒層8的氧氣、及來自上觸媒層1 4的氧氣,便將經由塔上 端的氣體排放口 1 8而排放出於反應塔2外。 本裝置係在利用使含過氧化氫之排水朝上流動而進行 處理的裝置中,於反應塔內將觸媒朝上下方向分割爲2層 (下觸媒層8與上觸媒層1 4)而配置,同時在二層之間形成 著空間部3 2,將在下觸媒層8中所產生的氧氣,於不致接 觸到上觸媒層1 4之情況下排放出於反應塔2外。藉此在上 觸媒層1 4中,便不致受到下觸媒層8所產生氧氣的阻礙, 而產生觸媒與過氧化氫間的接觸,結果便將提昇反應塔2 的過氧化氫去除率。 特別係因爲本裝置乃利用朝上流動而處理含過氧化氫 之排水,因此所產生的氧氣便將較容易從各觸媒層上方脫 除。此外,將所產生氧氣予以排放出的排氣管2 0係設置於 反應塔2內。相較於將排氣管2 0設置於反應塔2外之情況 (即,將排氣管20從外面連接於反應塔2之上觸媒層14 與下觸媒層8間的周壁部之情況),可將在下層觸媒層所產 生的氧氣良好的排放出於系統外。 另外,在本裝置中,支撐板1 0上所設置的排氣口 26與 集水口 2 4之設置數量及設置場所,在可充分保持著支撐板 1 〇強度的範圍之下,可進行任意設定。此情況下,因爲排 氣管20乃藉由氣體上升而產生對水的氣力揚昇(air lift) 12 31W發明說明書(補件)/92-03/91136694 I2263ll 欢果’因此爲使支撐板下端的排放水不致隨氣力揚昇而通 過排風管並到達上水面,所以必須設計配管徑。此外,集 水口 2 4乃依上觸媒層丨4觸媒不致掉落於下方之上,而將 ΰ徑縮小爲小於觸媒的大小,或者設置網孔狀或梳子狀的 篩網較爲恰當。 再者’最好使支撐板1 0之排氣口 2 6的下端開口位置, 位於較集水口 24下端開口位置更上方的位置處。藉由將支 撑板1 0非形成平板狀,而設定爲朝向排氣口 2 6的朝上方 向形狀(倒漏斗形狀),或在集水口 2 4周圍安裝著朝下方延 伸的管狀構件,便可使排氣口 2 6的下端位置,位於較集水 α 24更上方的位置處。 (實施例) 以下例示實施例。 利用圖3所模式性圖示的實驗裝置A、圖4所模式性圖 示的實驗裝置B,而檢驗本發明之效果。換句話說,準備 A,B二種系列之同一形狀反應塔,在實驗機A中實施依本 實施形態的中段排氣,而實驗機B則並未執行排氣,除此 之外的其餘條件均設定爲相同,而通過模擬含過氧化氫之 排水。另外,在圖3,4的實驗機A與B中,4 2係反應塔、 44係原水供應管、46係下觸媒層、48係上觸媒支撐板、 5 0係上觸媒、5 2係處理水排放管、5 4係連接於上觸媒支 撐板4 8排氣口上的排氣管(僅實驗機A有設置)、5 6係形 成於支撐板4 8上的集水口。此外,實驗機A與B規格係 如下述。 13 312/發明說明書(補件)/92_03/91136694 12263111226311 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to various types of treatment devices containing hydrogen peroxide drainage such as semiconductor manufacturing drainage and food container washing drainage. [Prior art] Hydrogen peroxide has excellent cleaning effect and sterilization effect, and because it is decomposed into oxygen and water washing chemicals after the reaction, it is widely used as a detergent and bactericide in the manufacturing process. For example, in a semiconductor device manufacturing plant, hydrogen peroxide will be used for wafer cleaning in various steps. Hydrogen peroxide used for cleaning and sterilization will be discharged as waste liquid (water containing hydrogen peroxide) from the manufacturing process. From the standpoint of having bactericidal power and substances that cause COD, it is best not to discharge this waste liquid directly into public waters. Although the treatment methods for the drainage containing hydrogen peroxide are known, although they are treated with reducing agents such as sodium sulfite or enzymes such as hydrogen peroxide, these methods have the potential to cause a large amount of drug use and increase running costs. In addition, a method of reducing hydrogen peroxide using a reduction catalyst such as activated carbon, a manganese-supported catalyst, or a platinum-supported catalyst is known. The hydrogen peroxide in the wastewater is decomposed into oxygen and water by contacting the reduction catalyst. By using such a reduction catalyst treatment method, it is possible to suppress and reduce the running cost required for the treatment of hydrogen peroxide-containing wastewater. The treatment using hydrogen peroxide-containing drainage using a reduction catalyst has the above advantages, but compared with the treatment using reducing agents and enzymes, this treatment will potentially have a problem that the treatment equipment will become larger. . 6 312 / Description of the Invention (Supplement) / 92-03 / 91136694 1226311 [Summary of the Invention] (Invention of the Invention) The present invention provides a method using a hydrogen peroxide decomposition catalyst (reduction catalyst) that can efficiently perform processing. Treatment device for hydrogen oxide drainage. The present invention relates to a processing device which circulates water containing hydrogen peroxide upwards in a reaction tower filled with a hydrogen peroxide decomposition catalyst, and decomposes the hydrogen peroxide into oxygen and hydrogen. The above-mentioned hydrogen peroxide decomposition catalyst is arranged in a plurality of layers in a vertical direction in a reaction tower. Then, the installer in the reaction mixture shall at least discharge the oxygen generated from the catalyst layer at the bottom to the exhaust pipe outside the reaction tower without contacting the catalyst layer above it. With this, the decomposition of hydrogen peroxide can be effectively performed. [Embodiment] (A preferred embodiment of the invention) First, in order to complete the present invention, the present invention will conduct the following discussions ① to ④. ① The reaction system using a catalyst generally improves the reaction efficiency by improving the contact efficiency between the catalyst and the reaction target (hydrogen peroxide in water in the present invention), and as a result, the device can be miniaturized, and Reduce equipment costs. ② In addition, a drainage treatment device containing hydrogen peroxide containing a reduction catalyst is used. In the reaction tower filled with the catalyst, the drainage water containing hydrogen peroxide flows upward or downward to continuously pass water, and the reaction proceeds from the reaction. It is common to obtain water treatment in the upper or lower part of the tower. Among them, when a high concentration of hydrogen peroxide is subjected to a decomposition treatment, a large amount of oxygen will be generated, and it will become a gas 312 / Invention Specification (Supplement) / 92-03 / 91136694 1226311 and cause sealing in the filling layer. From the viewpoint of the simplicity of the device structure and the safety of the system, it is best to choose an upward flow method that allows gas to be easily released from the upper part of the reaction tower. ③ However, it can be judged that the oxygen bubbles generated during the decomposition of hydrogen peroxide will reduce the contact efficiency between the catalyst and hydrogen peroxide, and as a result, the reaction efficiency of the treatment device will be reduced. Especially when dealing with the drainage with high concentration of hydrogen peroxide, for the reasons mentioned earlier, although it is best to use an upward flow reaction tower, the generated oxygen bubbles are rising in the catalyst layer. It is speculated that air bubbles will prevent the contact between the catalyst and the drainage. ④ Therefore, the present invention discusses a method for preventing the generated oxygen bubbles and hindering the contact between the catalyst and hydrogen peroxide. As a result, in a reaction tower that is treated by flowing the hydrogen peroxide-containing drainage water upward, the catalyst is divided into a plurality of layers in the vertical direction in the reaction tower, and the catalyst layer is arranged below the catalyst layer. Under the premise that the generated oxygen bubbles do not contact the upper catalyst layer, they are discharged from the reaction tower, so that the upper catalyst layer can generate the catalyst without being hindered by the oxygen gas bubbles generated by the lower catalyst layer. The contact with hydrogen peroxide has been found to increase the removal rate of hydrogen peroxide in the reaction tower. In addition, at this time, by setting the oxygen gas exhaust pipe in the reaction tower, it was found that the oxygen gas generated in the catalyst layer can be well discharged. The apparatus of this embodiment is a processing apparatus in which a hydrogen peroxide-containing decomposition catalyst is filled with a hydrogen peroxide-containing drainage flowing upward to pass water, and a hydrogen peroxide is decomposed into oxygen and water. Then, at least the oxygen generated in the catalyst layer at the bottom is set in the reaction tower, so as not to contact the catalyst layer above it 312 / Invention Specification (Supplement) / 92-03 / 91136694 8 1226311 The exhaust pipe is discharged outside the reaction tower ° In this case, although the number of layers to divide the hydrogen peroxide decomposition catalyst can be appropriately determined, it is usually 2 to 4 layers. In particular, it is divided into 2 layers as appropriate. Furthermore, the processing device of this embodiment has the largest amount of oxygen generated in the lowermost catalyst layer, so it is provided with an exhaust pipe that discharges at least the oxygen generated in the lowermost catalyst layer out of the reaction tower. 'But it would be more appropriate if the gas generated in each catalyst layer was discharged separately from the exhaust pipe outside the reaction tower. In addition, it is only necessary to use an exhaust pipe to discharge oxygen, as long as the generated oxygen bubbles can be effectively prevented, and the contact between the catalyst and hydrogen peroxide is blocked in the upper catalyst layer and emitted. Therefore, it is not necessary to exhaust all the gas generated in the catalyst layer, but it can also be partially emitted. In this embodiment, the type of the hydrogen peroxide decomposition catalyst is not limited, as long as the hydrogen peroxide can be reduced and decomposed into oxygen and water. Specific examples of the hydrogen peroxide decomposition catalyst include metal catalysts such as platinum, palladium, and manganese, or activated carbon. It is also possible to use a catalyst made of platinum, palladium, manganese, or the like on a base made of activated carbon, aluminum oxide, silicon oxide, or the like. Furthermore, in this embodiment, the catalyst charge of each catalyst layer that is divided into a plurality of layers in the vertical direction is divided into consideration. The concentration of hydrogen peroxide in the drainage, the drainage water flow rate, and the set flow rate are considered. It can be arbitrarily set under various factors such as the hydrogen oxide removal rate. In addition, different types of catalysts may be filled in the respective catalyst layers. 9 312 / Invention Specification (Supplement) / 92-03 / 91136694 1226311 The following describes the embodiments of the present invention with reference to the drawings. Fig. 1 is a schematic view showing an embodiment of a wastewater treatment device containing hydrogen peroxide according to the present invention. In FIG. 1, the reaction tower 2 is formed into a cylindrical shape. The raw water supply pipe 4 is fixed in a state of being inserted into the bottom of the reaction tower 2 from the outside. A supporting gravel layer 6 is provided in the bottom of the reaction tower 2, and the raw water supply pipe 4 is opened in the supporting gravel layer 6. On the supporting sand dish layer 6 in the reaction tower 2, a lower catalyst layer 8, an upper catalyst support plate 10, a supporting sand dish layer 1, 2, and an upper catalyst layer 14 are sequentially formed. The supporting gravel layers 6, 12 support the lower catalyst layer 8 and the upper catalyst layer 14 respectively, and are composed of large particles having a larger particle size than the catalyst particles constituting the lower catalyst layer 8 and the upper catalyst layer 14 Diameter support material. Furthermore, an L-shaped treatment water drain pipe 16 opened at the upper end is provided above the upper catalyst layer 14 and the treated water in the reaction tower 2 is overflowed and discharged (the upper part is sluiced water). In addition, a gas exhaust port 18 for exhausting the internal gas is provided at the upper end of the reaction tower 2. Then, an exhaust pipe 20 is provided through the catalyst supporting plate 10 above the reaction tower 2, the supporting gravel layer 12 and the upper catalyst layer 14. The lower end of the exhaust pipe 20 is supported by an upper catalyst support plate 10, and the upper end is supported by an exhaust pipe support 22 arranged at the upper end of the reaction tower 2. Among them, on the catalyst supporting plate 10 which supports the supporting gravel layer 12 and the upper catalyst layer 14, eight water collecting ports (collecting nets) 24 and four exhaust ports 26 shown in FIG. 2 are provided. Each exhaust port 26 is connected to the lower end of the exhaust pipe 20, respectively. In other words, in FIG. 1, although only one exhaust pipe 2 is shown, the exhaust pipe 20 is provided corresponding to each exhaust port 26, and a total of four exhaust pipes 2 are provided in this device. 0. In addition, these exhaust pipes 20 pass through the upper catalyst layer 14 and open above the treated water surface 30 at the upper end of the tower. 10 312 / Description of the Invention (Supplement) / 92-03 / 9113 6694 1226311 In other words, the upper end of the exhaust pipe 20 will reach the upper opening of the upper end of the treated water discharge pipe 16. In addition, the upper catalyst support plate 10 is disposed above the lower catalyst layer 8, and a space portion 32 will be formed between the lower catalyst layer 8 and the upper catalyst support plate 10. In this way, in this device, the catalyst layer is divided into upper and lower layers (lower catalyst layer 8 and upper catalyst layer 1 4) and is arranged in the reaction tower 2 and beside the upper catalyst layer 14 Exhaust pipe 20 for bypass. In this device, the hydrogen peroxide-containing drainage 28 is supplied to the lower end of the reaction tower 2 through the raw water supply pipe 4. A supporting gravel layer 6 is provided at the lower end of the reaction tower 2. The drainage containing hydrogen peroxide is in the supporting gravel layer 6 and diffuses throughout the entire area inside the reaction tower 2. As described above, a support plate 10 of the upper catalyst layer 14 is provided in the middle section of the reaction tower 2, and a space portion 32 is formed below the support plate 10. At the same time, a supply plate is provided on the support plate 10 as described above. The exhaust ports 26 for oxygen generated by the lower catalyst layer 8 are collected. Therefore, the exhaust port 26 is connected to the exhaust pipe 20 extending above the catalyst layer 8 below the upper end of the reaction tower 2. Therefore, this exhaust pipe 20 will pass some or all of the oxygen generated in the lower catalyst layer 8 from the exhaust port 26 of the support plate 10 to the upper catalyst layer 1 through the exhaust pipe 20. 4 upper end, and without contact with the catalyst of the upper catalyst layer 14 is discharged out of the system. Furthermore, the support plate 10 in the middle section of the reaction tower is provided with an additional water collecting port 24 for guiding the discharged water to the upper catalyst layer 14 different from the exhaust port 26. After removing some or all of the gas-discharged water, it will pass through the water collection port 24 to pass water into the upper catalyst layer 14 and the hydrogen peroxide in the discharged water will be 11 312 / Invention Specification (Supplement) / 92- 03/91136694 1226311 will be further reduced. The discharged water through the upper catalyst layer 14 will reach the water surface 30 at the upper end of the tower and be discharged out of the reaction tower 2 through the treated water discharge pipe 16. Oxygen from the lower catalyst layer 8 and oxygen from the upper catalyst layer 14 which are guided to the upper surface of the water through the exhaust pipe 20 are discharged from the reaction tower 2 through the gas discharge port 18 at the upper end of the tower. outer. In this device, the catalyst is processed by flowing the drainage containing hydrogen peroxide upward, and the catalyst is divided into two layers in the vertical direction in the reaction tower (lower catalyst layer 8 and upper catalyst layer 1 4). In the configuration, at the same time, a space portion 32 is formed between the two layers, and the oxygen generated in the lower catalyst layer 8 is discharged out of the reaction tower 2 without contacting the upper catalyst layer 14. Thereby, in the upper catalyst layer 14, the oxygen generated by the lower catalyst layer 8 will not be hindered, and the contact between the catalyst and the hydrogen peroxide will be generated. As a result, the hydrogen peroxide removal rate of the reaction tower 2 will be improved. . In particular, because this device uses upward flow to treat hydrogen peroxide-containing drainage, the generated oxygen will be more easily removed from above the catalyst layers. In addition, an exhaust pipe 20 for discharging the generated oxygen is installed in the reaction tower 2. Compared with the case where the exhaust pipe 20 is provided outside the reaction tower 2 (that is, the case where the exhaust pipe 20 is connected from the outside to the peripheral wall portion between the catalyst layer 14 and the lower catalyst layer 8 above the reaction tower 2 ), The good emission of oxygen generated in the lower catalyst layer can be out of the system. In addition, in this device, the number and locations of the exhaust ports 26 and the water collecting ports 24 provided on the support plate 10 can be arbitrarily set within a range that can sufficiently maintain the strength of the support plate 10. . In this case, because the exhaust pipe 20 rises through the gas, an air lift to the water (air lift) 12 31W Invention Specification (Supplement) / 92-03 / 91136694 I2263ll Pleasure fruit 'is therefore the lower end of the support plate The discharged water will not pass through the exhaust pipe and reach the water surface with the rise of air power, so the piping diameter must be designed. In addition, the water collecting port 24 is based on the upper catalyst layer. The catalyst does not fall below it, and the diameter is reduced to be smaller than the size of the catalyst, or a mesh or comb-shaped screen is more appropriate. Furthermore, it is preferable that the lower end opening position of the exhaust port 26 of the support plate 10 is located above the lower end opening position of the water collecting port 24. Instead of forming the support plate 10 into a flat plate shape, the support plate 10 can be set in an upward direction toward the exhaust port 26 (inverted funnel shape), or a tubular member extending downward around the water collecting port 24 can be installed. The lower end position of the exhaust port 26 is positioned higher than the water collecting α 24. (Examples) Examples are described below. The experimental device A schematically shown in Fig. 3 and the experimental device B schematically shown in Fig. 4 were used to check the effect of the present invention. In other words, prepare the same series of reaction towers of A and B series, and implement the middle stage exhaust according to this embodiment in the experimental machine A, but the experimental machine B does not perform the exhaust. Both are set to be the same, but by simulating drainage with hydrogen peroxide. In addition, in the experimental machines A and B of FIGS. 3 and 4, the 4 2 series reaction tower, the 44 series raw water supply pipe, the 46 series lower catalyst layer, the 48 series upper catalyst support plate, the 50 series upper catalyst, and 5 2 series of treated water discharge pipes, 5 4 series of exhaust pipes connected to the upper catalyst support plate 4 8 exhaust port (only provided for experimental machine A), 5 6 series of water collection ports formed on the support plate 4 8. The specifications of the experimental machines A and B are as follows. 13 312 / Invention Specification (Supplement) / 92_03 / 91136694 1226311

實驗機A 排氣機構:有 排氣機構規格 排氣口 : 1個(支撐板中央、口徑1 5mm)Testing machine A Exhaust mechanism: Yes Exhaust mechanism specifications Exhaust port: 1 (center of support plate, diameter 15 mm)

實驗機B 排氣機構:無 實驗機A與B之共同規格 反應塔徑:7 0 m m 所使用之過氧化氫觸媒:錳載持觸媒 觸媒塡充高度:上下各5 0 0mm 觸媒塡充量:上下各192mL 集水口 : 6個(口徑2 m m ) 通水量:770mL/hr、1540mL/hr、3080mL/hr 通水速度:SV = 2/hr、4/hr、8/hr 模擬排放水:過氧化氫濃度:2 00 OOmg/L (在純水中溶解著 試藥的過氧化氫水溶液,並利用氫氧化鈉調 整爲 ρΗ=10·5) 經上述比較實驗而所獲得各實驗機的經處理後之過氧 化氫濃度及過氧化氫去除率,如表1所示。如表1所示, 實驗機Α的經處理後之過氧化氫濃度及過氧化氫去除率, 均較實驗機B在該等各個通水條件之情況下爲之上升。換 句話說,確認到藉由依使從下觸媒層所產生氧氣的其中一 部份或全部不致到達上觸媒層之方式,而從反應塔中段導 向於系統外面,便可在同一觸媒量與通水條件之下,提昇 14 312/發明說明書(補件)/92-03/91136694 1226311 處理水水質與過氧化氫去除率。 表1 通水速度 經處理過之過氧化氫 濃度 過氧化氫去除率 實驗機A(有排氣) S V = 2 ( / h r ) 0 m g / L 1 0 0 % 貫驗機A (有排氣) S V = 4 ( / h r ) 0 m g / L 1 0 0 % 實驗機A(有排氣) S V = 8 (/ h r ) 5 m g / L 9 9.9 8 % 實驗機B (無排氣) S V = 2 (/ h r ) 2 2 m g / L 9 9.8 9 % 實驗機B (無排氣) S V = 4 ( / h r ) 7 9 m g / L 9 9.61% 實驗機B (無排氣) S V = 8 (/ h r ) 5 2 0 m g / L 9 7.4 0% 如上述,本實施形態的含有過氧化氫之排水處理裝置, 便可提高過氧化氫分解觸媒與過氧化氫間的接觸效率,並 達裝置小型化、省空間、降低設備費的功效。 【圖式簡單說明】 圖1爲本發明含有過氧化氫之排水處理裝置一實施形態 槪略圖。 圖2爲圖1所示裝置之上層觸媒支撐板平面圖。 圖3爲實驗例中所採用實驗裝置槪略圖。 15 312/發明說明書(補件)/92-03/91136694 1226311 圖4爲實驗例中所採用實驗裝置槪略圖。 (元件符 號說明 ) 2 反 應 塔 4 原 水 供 jm 管 6 支 撐 砂 礫 層 8 下 觸 媒 層 10 上 觸 媒 支 撐板 12 支 撐 砂 礫 層 14 上 觸 媒 層 16 處 理 水 排放 管 18 氣 體 排 放 □ 20 排 氣 管 22 排 氣 管 支 撐 體 24 集 水 □ 26 排 氣 □ 28 含 過 氧 化 氫 之排水 30 處 理 水 水 面 32 空 間 部 42 反 應 塔 44 原 水 供 應 管 46 下 觸 媒 層 48 上 觸 媒 支 撐 板 50 上 觸 媒 52 處 理 水 排 放 管 312/發明說明書(補件)/92-03/9113 6694 1226311Exhaust mechanism of experimental machine B: No common reaction tower of experimental machines A and B. Diameter of the reactor: 70 mm. Hydrogen peroxide catalyst used: Manganese-supported catalyst catalyst. Filling height: 50 mm above and below the catalyst.塡 Filling capacity: 192mL upper and lower water collecting ports: 6 (caliber 2 mm) Water flow rate: 770mL / hr, 1540mL / hr, 3080mL / hr Water flow rate: SV = 2 / hr, 4 / hr, 8 / hr simulated discharge Water: Hydrogen peroxide concentration: 2,000 mg / L (aqueous hydrogen peroxide solution in which the reagent is dissolved in pure water, and adjusted to ρΗ = 10 · 5 with sodium hydroxide) Each experimental machine obtained through the above comparative experiment The treated hydrogen peroxide concentration and hydrogen peroxide removal rate are shown in Table 1. As shown in Table 1, the treated hydrogen peroxide concentration and hydrogen peroxide removal rate of the experimental machine A are higher than those of the experimental machine B under these various water-passing conditions. In other words, it was confirmed that the same amount of catalyst can be used at the same amount of catalyst by guiding part or all of the oxygen generated from the lower catalyst layer not to reach the upper catalyst layer, and leading the outside of the system from the middle of the reaction tower. Under the conditions of water flow, improve 14 312 / Invention Specification (Supplement) / 92-03 / 91136694 1226311 Treated water quality and hydrogen peroxide removal rate. Table 1 Hydrogen peroxide concentration after treatment of water flow rate Hydrogen peroxide removal rate test machine A (with exhaust) SV = 2 (/ hr) 0 mg / L 1 0 0% Test machine A (with exhaust) SV = 4 (/ hr) 0 mg / L 1 0 0% Tester A (with exhaust) SV = 8 (/ hr) 5 mg / L 9 9.9 8% Tester B (without exhaust) SV = 2 ( / hr) 2 2 mg / L 9 9.8 9% Tester B (without exhaust) SV = 4 (/ hr) 7 9 mg / L 9 9.61% Tester B (without exhaust) SV = 8 (/ hr) 5 2 0 mg / L 9 7.4 0% As described above, the wastewater treatment device containing hydrogen peroxide in this embodiment can improve the contact efficiency between the hydrogen peroxide decomposition catalyst and the hydrogen peroxide, and achieve device miniaturization, The effect of saving space and reducing equipment costs. [Brief description of the drawings] FIG. 1 is a schematic view of an embodiment of a wastewater treatment device containing hydrogen peroxide according to the present invention. FIG. 2 is a plan view of an upper catalyst support plate of the device shown in FIG. 1. FIG. FIG. 3 is a schematic diagram of an experimental device used in an experimental example. 15 312 / Invention Specification (Supplement) / 92-03 / 91136694 1226311 Figure 4 is a schematic diagram of the experimental device used in the experimental example. (Description of element symbols) 2 Reaction tower 4 Raw water supply jm pipe 6 Supporting gravel layer 8 Lower catalyst layer 10 Upper catalyst support plate 12 Supporting gravel layer 14 Upper catalyst layer 16 Processing water discharge pipe 18 Gas discharge □ 20 Exhaust pipe 22 Exhaust pipe support 24 Water collection □ 26 Exhaust □ 28 Drainage with hydrogen peroxide 30 Water surface for treatment 32 Space section 42 Reaction tower 44 Raw water supply pipe 46 Lower catalyst layer 48 Upper catalyst support plate 50 Upper catalyst 52 treated water discharge pipe 312 / Invention Manual (Supplement) / 92-03 / 9113 6694 1226311

54 排氣管 56 集水口 312/發明說明書(補件)/92-03/91136694 1754 Exhaust pipe 56 Water collecting port 312 / Invention manual (Supplement) / 92-03 / 91136694 17

Claims (1)

Ϊ22§31h \ - 請春灘纖匯 1 . 一種含有過氧化氫之排水處理裝置,係在塡充著過氧 化氫分解觸媒的反應塔內,將含過氧化氫之排水朝向流動 的進行通水,並將過氧化氫分解爲氧與水的處理裝置;其 中,上述過氧化氫分解觸媒係在反應塔內,朝上下方向分 割爲複數層而配置著,同時在反應塔內設置著至少將最下 端之觸媒層所產生的氧氣,在不致接觸到較其上方之觸媒 層的情況下,便排放出於反應塔外的排氣管。 2 .如申請專利範圍第1項之含有過氧化氫之排水處理裝 置,其中,在反應塔內設置著將各觸媒層所產生的氧氣, 分別在不致接觸到較其上方之觸媒層的情況下,便排放出 於反應塔外的排氣管。 3 .如申請專利範圍第2項之含有過氧化氫之排水處理裝 置,其中,上述排氣管下端係下端支撐於未接觸到上述氣 體並支撐著上方觸媒層的支撐板上。 4 ·如申請專利範圍第3項之含有過氧化氫之排水處理裝 置,其中,上述排氣管下端係連接於上述支撐板上所設置 的排氣口。 5 ·如申請專利範圍第4項之含有過氧化氫之排水處理裝 置,其中,在上述最下端觸媒層與上述支撐板之間係有空 間,透過此空間便將收集在上述最下端觸媒層中所產生的 氣體,並集中於上述排氣管中。 6 .如申請專利範圍第4項之含有過氧化氫之排水處理裝 置,其中,上述支撐板設有將來自下方的排放水導向於上 18 312/發明說明書(補件)/92-03/91136694 1226311 方觸媒層的集水口。 7 .如申請專利範圍第 4項之含有過氧化氫之排水處理裝 置,其中,上述排氣管上端係在反應塔內的水面上呈開口 著。Ϊ22§31h \-Please Chuntan Fibre Exchange 1. A drainage treatment device containing hydrogen peroxide is placed in a reaction tower filled with hydrogen peroxide decomposition catalyst, and the drainage water containing hydrogen peroxide is directed to flow. A treatment device for water and decomposing hydrogen peroxide into oxygen and water. The catalyst for decomposing hydrogen peroxide in the reaction tower is divided into a plurality of layers in a vertical direction and arranged at the same time. The oxygen generated from the catalyst layer at the lower end will be discharged from the exhaust pipe outside the reaction tower without contacting the catalyst layer above it. 2. The wastewater treatment device containing hydrogen peroxide according to item 1 of the scope of the patent application, wherein the reaction tower is provided with oxygen generated by each catalyst layer so as not to contact the catalyst layer above it. In this case, the exhaust pipe outside the reaction tower is discharged. 3. The drainage treatment device containing hydrogen peroxide according to item 2 of the scope of the patent application, wherein the lower end of the exhaust pipe is supported on a support plate that does not contact the gas and supports the upper catalyst layer. 4. The drainage treatment device containing hydrogen peroxide according to item 3 of the patent application scope, wherein the lower end of the exhaust pipe is connected to an exhaust port provided on the support plate. 5. If there is a hydrogen peroxide-containing drainage treatment device in item 4 of the scope of patent application, there is a space between the lowermost catalyst layer and the support plate, and the lowermost catalyst will be collected through this space. The gas generated in the layer is concentrated in the above-mentioned exhaust pipe. 6. The drainage treatment device containing hydrogen peroxide according to item 4 of the scope of patent application, wherein the support plate is provided with a guide for discharging water from below to the upper 18 312 / Invention Specification (Supplement) / 92-03 / 91136694 1226311 Catchment for square catalyst layer. 7. The drainage treatment device containing hydrogen peroxide according to item 4 of the scope of patent application, wherein the upper end of the exhaust pipe is open on the water surface in the reaction tower. 19 312/發明說明書(補件)/92-03/9113669419 312 / Invention Specification (Supplement) / 92-03 / 91136694
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