1250132 九、發明說明： 發明所屬之技術領域 本發明係關於半導體、液晶顯示器（LCD)等相關工業製 程排放廢水’甚至其它事業所產生的含有機污染物之廢水 的有機物的氧化去除，是關於一種藉由注入臭氧及經紫外 光照射之廢水中有機物氧化去除流程與系統。 先前技術 國内目前1C及LCD製造等高科技產業發展迅速，清 洗步驟佔整體製程30%以上，且隨著製程精微化及基板尺 寸放大，所排放的有機廢水量與日遽增，加上目前科學園 區管理局要求廠商製程水回收率舊廠需75%，新設廠需 8 5 %以上，故申請人先前已進行專利申請「廢水中有機物 氧化去除系統與方法」（美國專利US2003-0106855A1，目 前己收到核准通知），利用一個或數個紫外線/臭氧氧化去除 模組處理有機排放廢水，但此系統在處理不含發泡性物質 之有機廢水具相當成效。此美國專利US2003-0106855A1 所使用之氣液分離器（Degassing separator)為離心式氣液分 離器，例如美國GDT water process corporation生產之 GDTTM氣液分離器（US patent 5674321)，其使用316L不鏽 鋼組成，内部採旋滿離心裝置破壞泡泳使成為液態狀往下 排放，氣體較輕則上升排至臭氧破壞器。惟日前興起之光電 產業其清洗製程多添加界面活性劑或清潔劑等有機化學藥 品，含有泡沫、水氣及未溶解於廢水中的臭氧及其他氣體， 1250132 k原模、、且中的疋壓閥至氧液分離器時，因離心式氣液分 離1"無法順利分離泡沫、水氣及溶解之臭氧及其他氣體， 使付部份泡沫直接流向臭氧破壞器而導致臭氧破壞器有排 水溢出，無法達到臭氧破壞器及氧化去除模組之原有功能。 發明内容 本毛明的一主要目的在提出一種廢水中有機物的紫外 線/臭氧氧化去除模組，其可以解決料性有機廢水所造成 臭氧破壞器溢水現象，以達到紫外線/臭氧氧化模組可廣泛 處理半導體及LCD廠等清洗製程所排放有機廢水將其中有 機物去除的目的。 本發明之一種廢水中有機物的氧化去除模組，包含： 一臭氧吸入器，其適於分別連接一用於栗入欲被處理 水的馬達’及-臭氧產生器，該臭氧吸入器用於混合該欲 被處理水與臭氧來源氣體； 一臭氧溶解槽，其接收該臭氧吸入器所產生的臭氧/廢水 混合液，並提供臭氧與該欲被處理水中的有機物進行氧化 反應的一停留時間； 連接於該臭氧溶解槽頂部的一離心式氣液分離器〜 連接於該離d氣液分離器的定壓閥，_連接於該定壓問 的吸附式氣液分離器，及連接於該氣液分離器的一臭氧破 壞器’其中該離心式氣液分離器接收由該臭氧溶解槽頂部 流出的臭氧、水氣及泡沫’且破壞泡珠使成為液態水；节 定壓閥將該離心式氣液分離器内的臭氧、水氣及泡床固定 1250132 於-設定壓力，並使大於該設定壓力之臭氧、水氣及殘餘 泡沐排出至該吸附式氣液分離〜；該吸附式氣液分離器 内含-吸附材料，將料、水氣與部分臭氧吸附，增加它 們在吸附式氣液分離器内的停留時間，於是由該吸附式氣 液分離器底部排出液態水及由其頂部排出未溶於水的臭氧 及其他氣體至該臭氧破壞器； 一紫外線反應槽，其接收來自該臭氧溶解槽的含臭氧 之廢水，並且使該含臭氧之廢水經紫外光照射使其中的 有機物進行光化學氧化； 一選擇性的附加純化元件，該附加純化元件為薄膜處 理兀件、離子交換元件、活性碳吸附元件、或脫氣元件， 用於將紫外線反應槽出流水進一步純化；及 一迴流機構，包含用於將該紫外線反應檜的出流水或 當該附加純化元件存在時將該附加純化元件的出流水的一 部份迴流至該欲被處理水的管路而構成其中的一部份的迴 流管路，將另一部份出流水出流至下一處理階段的出流管 路，及一或多個閥用於控制迴流水對至下一處理階段的出 流水的流量比例。 較佳的，該吸附材料為活性碳。 較佳的，該吸附式氣液分離器内含一用於支持該吸附 材料的篩網，以防止該吸附材料流出該吸附式氣液分離器。 較佳的，該離心式氣液分離器破壞泡沫所形成的液態 水被排回至該臭氧吸入器之前與該該欲被處理水合併。 較佳的，該迴流機構包含位於該出流管路上的一流量 1250132 控制閥，位於該迴流管路上的另一流量控制閥，及一設於 該迴流管路進入該欲被處理水的管路之前的用於防止該欲 被處理水進入該迴流管路的逆止閥。 本發明亦提出一種廢水中有機物氧化去除系統，包含 複數個連續串聯的前述本發明模組或進一步包含介於其中 兩相鄰模組中的一或多個串連的附加純化元件，該附加純 化元件為薄膜處理元件、離子交換元件、活性碳吸附元件、 或脫氣元件，其用於將前一階段出流水進一步處理。 實施方式 目前咼科技產業清洗製程常使用的界面活性劑或清潔 劑等泡沫性有機廢水，本發明提出一種此類泡沫性有機廢 水的有機物的氧化去除模組。依本發明的一較佳具體實施 例而完成的一種廢水中有機物的氧化去除模組被示於圖i 及2,其中馬達1將被處理水加壓輸送至臭氧吸入器2,臭氧 吸入益2可將氣體吸人舆水流混合，此裝置材質為抗臭氧腐 蝕之材質在此I由馬達1與一流量控制閥門9之調整，可 吸入不同流量之臭氧氣體。 臭氧氣體由臭氧產生器3產出並 吸入器2所混合臭氧與廢水之 臭氧溶解槽4，其提供了氣體 提供至臭氧吸入器2。該臭氧 臭氧/廢水混合液接著進入_ 接觸的時間和空間，臭產、、六 吳氧命解槽4為316 L不鏽鋼材質| 成，或其他抗臭氧腐蝕之松新 ^ . ^ t <材貝。當臭氧與廢水氧化時產j 強大泡沫、水氣及未溶舷 、 解於廢水中的臭氧及其他氣體，另 它們由臭氧溶解槽4的頂邻塞 貝4 ^入一離心式氣液分離器5，j 1250132BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the oxidative removal of organic matter from wastewater containing organic pollutants produced by semiconductors, liquid crystal displays (LCDs) and other related industrial processes, and even other businesses. The process and system are removed by oxidation of organic matter in wastewater injected with ozone and ultraviolet light. Prior art Domestic high-tech industries such as 1C and LCD manufacturing are developing rapidly, and the cleaning steps account for more than 30% of the overall process. With the miniaturization of the process and the enlargement of the substrate size, the amount of organic wastewater discharged is increasing day by day. The Science Park Administration requires that the manufacturer's process water recovery rate of the old factory needs 75%, and the new plant needs more than 85 %. Therefore, the applicant has previously applied for a patent application "System and Method for Oxidation and Removal of Organic Matter in Waste Water" (US Patent US2003-0106855A1, currently The approval notice has been received to treat the organic discharge wastewater by one or several UV/ozone oxidation removal modules, but the system is quite effective in treating organic wastewater containing no foaming substances. The degassing separator used in this US patent US2003-0106855A1 is a centrifugal gas-liquid separator, such as a GDTTM gas-liquid separator (US patent 5674321) manufactured by GDT water process corporation of the United States, which is composed of 316L stainless steel. The internal centrifugal full centrifuge device destroys the bubble so that it is discharged in a liquid state, and when the gas is light, it is discharged to the ozone destroyer. However, the photovoltaic industry, which has recently emerged, has added organic chemicals such as surfactants or detergents to its cleaning process. It contains foam, water vapor and ozone and other gases that are not dissolved in wastewater. The 1250132 k original mold and the rolling pressure When the valve is to the oxygen liquid separator, the centrifugal gas-liquid separation 1" cannot smoothly separate the foam, moisture and dissolved ozone and other gases, so that part of the foam flows directly to the ozone destroyer, causing the ozone destroyer to overflow. The original function of the ozone destroyer and oxidation removal module cannot be achieved. SUMMARY OF THE INVENTION A main purpose of the present invention is to propose an ultraviolet/ozone oxidation removal module for organic matter in wastewater, which can solve the phenomenon of ozone breaker overflow caused by organic wastewater, so that the ultraviolet/ozone oxidation module can be widely processed. The organic waste water discharged from the cleaning process such as semiconductor and LCD factory will remove organic matter. An oxidation removal module for organic matter in wastewater according to the present invention comprises: an ozone inhaler adapted to respectively connect a motor for pumping water to be treated and an ozone generator for mixing the ozone inhaler a water and ozone source gas to be treated; an ozone dissolution tank that receives the ozone/waste water mixture produced by the ozone inhaler and provides a residence time for the oxidation reaction of ozone with the organic matter in the water to be treated; a centrifugal gas-liquid separator at the top of the ozone dissolution tank is connected to the constant pressure valve of the gas separation liquid separator, is connected to the adsorption type gas-liquid separator of the constant pressure, and is connected to the gas-liquid separation An ozone destroyer of the apparatus, wherein the centrifugal gas-liquid separator receives ozone, water vapor and foam flowing out from the top of the ozone dissolution tank and destroys the beads to become liquid water; the fixed pressure valve uses the centrifugal gas-liquid The ozone, water vapor and bubble bed in the separator fixes 1250132 at a set pressure, and discharges ozone, moisture and residual bubbles larger than the set pressure to the adsorption gas-liquid separation~; The attached gas-liquid separator contains an adsorbent material, which adsorbs the material, the water gas and a part of the ozone, and increases their residence time in the adsorption gas-liquid separator, so that the liquid water is discharged from the bottom of the adsorption gas-liquid separator and Discharging water-insoluble ozone and other gases from the top to the ozone destroyer; an ultraviolet reaction tank receiving ozone-containing wastewater from the ozone dissolution tank, and irradiating the ozone-containing wastewater with ultraviolet light The organic substance is subjected to photochemical oxidation; a selective additional purification element, which is a thin film processing element, an ion exchange element, an activated carbon adsorption element, or a degassing element, for further purifying the outflow water of the ultraviolet reaction tank; And a reflow mechanism comprising an outlet water for reacting the ultraviolet ray or a portion of the outlet water of the additional purification element when the additional purification element is present, flowing back to the pipeline of the water to be treated a part of the return line, the other part of the outflow water is discharged to the outflow line of the next processing stage, and one or more valves are used for control The return water flow ratio of water to the next stage of processing. Preferably, the adsorbent material is activated carbon. Preferably, the adsorption gas-liquid separator comprises a screen for supporting the adsorbent material to prevent the adsorbent material from flowing out of the adsorption gas-liquid separator. Preferably, the centrifugal gas-liquid separator destroys the liquid water formed by the foam and is combined with the water to be treated before being discharged back to the ozone inhaler. Preferably, the recirculation mechanism comprises a flow rate 1250132 control valve located on the outlet line, another flow control valve located on the return line, and a line disposed in the return line to enter the water to be treated The previous check valve for preventing the water to be treated from entering the return line. The present invention also provides an organic matter oxidation removal system in wastewater, comprising a plurality of consecutively connected series of the inventive modules or an additional purification element further comprising one or more of two adjacent modules in series, the additional purification The element is a thin film processing element, an ion exchange element, an activated carbon adsorption element, or a degassing element for further processing the water from the previous stage. Embodiments Currently, a foaming organic waste water such as a surfactant or a cleaning agent which is often used in a cleaning process of the 咼 industry, the present invention proposes an oxidative removal module for an organic substance of such a foamed organic waste water. An oxidation removal module for organic matter in wastewater according to a preferred embodiment of the present invention is shown in Figures i and 2, wherein the motor 1 is pressurized to be delivered to the ozone inhaler 2 by the treated water, and the ozone inhalation benefit 2 The gas can be mixed with the water flow, and the device is made of anti-ozone corrosion material. The I is adjusted by the motor 1 and a flow control valve 9 to absorb different ozone gases. Ozone gas is produced by the ozone generator 3 and is mixed with ozone and wastewater in the ozone dissolving tank 4 of the inhaler 2, which supplies gas to the ozone inhaler 2. The ozone ozone/wastewater mixture then enters the time and space of contact, the odor production, and the Liuwu oxygen solution tank 4 is 316 L stainless steel material | into, or other anti-ozone corrosion pine new ^. ^ t < shell. When ozone and wastewater are oxidized, strong foam, moisture and undissolved, ozone and other gases in the wastewater are produced, and they are separated from the top of the ozone dissolution tank 4 by a centrifugal gas-liquid separator. 5,j 1250132
形成液態水流回該臭氧吸入器2的 合。一具定壓閥6將該離心式氣液分 丨，並可使大於所設定壓力之臭氧、 一吸附式氣液分離器7,再連接至一 、 4 8 °該吸附式氣液分離器7可分離水氣及泡沫， 避免水進入該臭氧破壞器8。臭氧破壞器8的目的是將排出 亂體中的臭氧破壞。廢水經臭氧溶解槽4流出後進人紫外線 (UV )反應槽9進行紫外光輻射氧化反應，槽體内的燈 官y對流經槽體的水進行光化學氧化反應，此處使用的為 中壓汞燈，而在實施上亦可使用低壓或高壓汞燈。該流量 控制閥門1G設在紫外線反應槽9出口，藉此可控制臭氧吸入 器2的後端出口壓力。一迴流管路u，接在該流量控制閥門 9後，其將處理後水樣一部份再送回到馬達i前與未處理的 廢水混合，#此以稀釋水中的T〇c濃度，並增加廢水的停 留時間；迴流管路流至馬達！前安裝—逆止閥12避免未處理 之廢水流進迴流管路中。另一流量控制閥門13設在迴流管 路11上，藉此可控制迴流與出流比例，本系統之迴流比(迴 流比=迴流水量：出流水量）控制於〇 5」〜2〇 : ι之間。 該吸附式氣液分離器7可公Μ I名Ώ、nThe liquid water is formed to flow back to the ozone inhaler 2. A constant pressure valve 6 divides the centrifugal gas and liquid, and can make ozone, an adsorption type gas-liquid separator 7 larger than the set pressure, and then connect to the adsorption gas-liquid separator 7 at a temperature of 4, 4 8 °. The water vapor and foam can be separated to prevent water from entering the ozone destroyer 8. The purpose of the ozone destroyer 8 is to destroy the ozone in the disordered body. The wastewater flows out through the ozone dissolution tank 4 and enters the ultraviolet (UV) reaction tank 9 for ultraviolet radiation oxidation reaction. The lamp body y is used to photochemically oxidize the water flowing through the tank, and the medium pressure mercury is used here. Lights, and low pressure or high pressure mercury lamps can also be used in implementation. The flow control valve 1G is provided at the outlet of the ultraviolet reaction tank 9, whereby the outlet pressure of the rear end of the ozone inhaler 2 can be controlled. a return line u, after being connected to the flow control valve 9, it mixes the treated water sample back to the motor i before mixing with the untreated wastewater, thereby diluting the concentration of T〇c in the water and increasing The residence time of the wastewater; the return line flows to the motor! Front Mounting - Check valve 12 prevents untreated wastewater from flowing into the return line. Another flow control valve 13 is provided on the return line 11 to control the reflux and outflow ratio. The reflux ratio of the system (reflux ratio = reflux water amount: outflow amount) is controlled at 」5"~2〇: ι between. The adsorption type gas-liquid separator 7 can be publicized.
/擎命/的緩衝槽體。 水氣與部分臭氧吸附 1250132 於活性碳，增加停留時間，使得其中的泡沫破滅轉換成水， 未溶於水的臭氧及其他氣體再排至臭氧破土襄器8，將其中的 臭乳轉換為〇 2排出。該臭氧破壞器8的緩衝槽較佳的具有一 可被打開的槽蓋’以利於該活性碳或其它吸附材料之更 換及緩衝槽的底部裳有8〇篩目（mesh)不鑛鋼筛網η防止 活性碳之流失。 圖3為將圖1巾的氧化去除模組進-步安裝其他純化元 件14之變化應用方式。該流量控制閥門9後之出流水再進入 其他純化元件14，>薄膜處理元件、離子交換元件、活性 碳吸附元件、脫氣元件等， 丨卞寻J將水中或氧化反應產生的離 子類物質、顆粒性物質、或因溶解過程產生的過飽和氣體 去除。 對照例 其總有機 取實廠含界面活性劑之有機廢水進行實驗 碳（TOC)濃度為22ppm。 使用美國專利us勒·嶋855A1 w丨的先前技 =紫外線氧化系統對前述有機廢水進行有機物去^實 2 ’臭减人器内的臭氧/廢水混合液的臭氧濃度維 乂5 ppm。系統經運轉3分箱始自知 〇 得3刀鐘後，臭乳破壞器溢出廢水，季 統無法運轉而需關閉。 系 實施例 統對前述有機廢水 以本發明圖1的臭氧/紫外線氧化系 1250132 - 貝微條件同對照例。 實驗結果為廢水總有機碳濃度〇由22 0·5 ppm，且系統運 2 PPm降至 溢出的現象，且八:未再發生臭氧破壞器8有水 水管皆有小流心:此7的緩衝槽活性碳床下方的排 R排出’由此可見本發明達到預期之效果。 圖式簡單說明 圖1顯示依本發明的一較佳具體實施例而完成的-種 廢水中有機物的氧化去除模組的方塊流程圖。 圖2顯示圖i的氧化去除模組的一部份方塊流程圖。 圖3顯不依本發明的另一較佳具體實施例而完成的〜 種廢水中有機物的氧化去除模組的方塊流程圖。 主要元件之符號說明 I·馬達 2··臭氧吸入器 3··臭氧產生器 4·.臭氧溶解槽 5··離心式氣液分離器 6··定壓閥 7··吸附式氣液分離器 8 ··臭氧破壞器 9 ·.紫外線反應槽 1 〇，1 3 ··流量控制閥 12. _逆止閥 11··迴流管路 71··活性碳 72··筛網 11/Human life / buffer tank. Water vapor and some ozone adsorbed 1250132 on activated carbon, increasing the residence time, causing the foam to be broken into water, and the water-insoluble ozone and other gases were discharged to the ozone breaking device 8 to convert the scent into 〇 2 discharge. The buffer tank of the ozone destroyer 8 preferably has an openable tank cover 'to facilitate the replacement of the activated carbon or other adsorbent material and the bottom of the buffer tank is provided with 8 mesh mesh steel screen. η prevents the loss of activated carbon. Figure 3 is a variation of the application of the oxidative removal module of Figure 1 to other purification elements 14 in a step-by-step manner. The flow water after the flow control valve 9 is re-entered into the other purification element 14, > thin film processing element, ion exchange element, activated carbon adsorption element, degassing element, etc., to find the ionic species generated by water or oxidation reaction. , particulate matter, or supersaturated gas generated by the dissolution process. Comparative Example The total organic solvent of the organic surfactant containing the surfactant was subjected to an experimental carbon (TOC) concentration of 22 ppm. The ozone concentration of the ozone/wastewater mixture in the above-mentioned organic wastewater was reduced to 5 ppm using the prior art of the US patent us 嶋 855A1 w丨. The system started to operate after 3 minutes of operation. After 3 knives, the stink breaker broke the waste water, and the season could not be operated and needed to be closed. EXAMPLES The above organic wastewater was subjected to the ozone/ultraviolet oxidation system of Fig. 1 of the present invention. The experimental results show that the total organic carbon concentration of the wastewater is 22 0. 5 ppm, and the system transports 2 PPm to the overflow phenomenon, and 8: there is no reoccurrence of the ozone destructor. 8 There are small water cores in the water pipes: the buffer of this 7 The row R exiting below the tank activated carbon bed is thus seen to achieve the desired effect of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a block flow diagram showing an oxidation removal module for organic matter in wastewater in accordance with a preferred embodiment of the present invention. Figure 2 shows a block diagram of a portion of the oxidation removal module of Figure i. Figure 3 is a block flow diagram of an oxidation removal module for organic matter in a wastewater that is not completed in accordance with another preferred embodiment of the present invention. Symbols of main components I. Motor 2··Ozone inhaler 3·Ozone generator 4·Ozone dissolving tank 5··Centrifugal gas-liquid separator 6··Pressure valve 7··Adsorption type gas-liquid separator 8 ··Ozone destroyer 9 ·.UV reaction tank 1 〇,1 3 ··Flow control valve 12. _Check valve 11··Return line 71··Active carbon 72··Screen 11