1337982 (1) 九、發明說明 【發明所屬之技術領域】 本發明是關於使用逆滲透（R0)膜分離裝置處理從電 子設備製造工廠等所排出含有機物（TOC )排水的方法及 裝置。 【先前技術】 環境基準乃至水質基準有逐漸嚴格的傾向，對於排放 水同樣期待高度的淨化。從供水不足解除的目的，同時爲 了回收各種的排水再利用，期待著高度的水處理技術的開 發。 R0膜分離處理可以有效地除去水中的雜質（離子類 、有機物、微粒子等）。回收半導體製造過程所排出含丙 酮 '異丙醇等的高濃度T0C或者含低濃度T〇C排水再利 用時，將此首、先以生物處理除去TOC成分並將生物處理 水R0膜處理後淨化的方法記載於日本專利特開2002-3 3 6 8 8 6號公報。 生物處理排水通過R0膜分離裝置時，因微生物使有 機物分解生成生物代謝物，而使得R 0膜的膜面堵塞，降 低流通量。 不以生物處理直接使含TOC排水通過R0膜分離裝置 時’由於流入R0膜分離裝置的TOC濃度高，因此在R0 膜分離裝置內.._微_生物的_..繁_殖容易。從抑制R0膜分離裝置 內的生物污染的目的方面，通常是在含TOC排水內添加 (2) (2)1337982 多量的黏膜控制劑•但是黏膜控.制劑極爲昂貴。 從電子設備工廠所排出的排水，由於混入有附著在 R0膜分離裝置的膜面上，而有降低流通量之虞的非離子 性表面活性劑的場合，因此，以往以上含非離子性表面活 性劑斑水不能運用R 0膜分離處理。 來自電子設備工廠的排水中除了上述有機物以外同時 會有含過氧化氫等的氧化劑的場合。排水中含有氧化劑時 ，從利用氧化劑防止R0膜的氧化劣化的目的，一般是在 R0膜分離裝置的前段設置活性碳塔。該等排水中同時含 有機物，因此活性碳塔內容易成爲微生物的溫床。活性破 塔內一旦微生物繁殖時，使得活性碳塔的差壓上升，並且 導致微生物漏洩使得活性碳處理水的SDI値上升。 【發明內容】 本發明是提供利用 R0膜分離裝置處理·回收時，因 膜分離裝置內的有機物的膜面附著導致之流通量的降 低，防止生物污染長期間穩定進行處理的同時，有效地降 低水中TOC濃度獲得高水質之處理水的含有機物排水處 理方法及裝置爲目的β1337982 (1) Description of the Invention [Technical Field] The present invention relates to a method and apparatus for discharging organic-containing (TOC) water discharged from an electronic equipment manufacturing plant or the like using a reverse osmosis (R0) membrane separation apparatus. [Prior Art] Environmental standards and even water quality standards tend to be stricter, and high levels of purification are expected for discharge water. We are looking forward to the development of high-level water treatment technology for the purpose of eliminating the shortage of water supply and recycling various types of drainage. The R0 membrane separation treatment can effectively remove impurities (ions, organics, fine particles, etc.) from the water. When recycling high-concentration T0C containing acetone 'isopropyl alcohol or the like discharged from the semiconductor manufacturing process or draining with low concentration T〇C, the first and first biological treatments are used to remove the TOC component and the biological treatment water R0 membrane is treated and purified. The method is described in Japanese Patent Laid-Open No. 2001-3 3 6 8 8 . When the biological treatment drainage passes through the R0 membrane separation device, the microorganisms cause the organic matter to decompose to form a biological metabolite, which causes the membrane surface of the R 0 membrane to clog and reduce the amount of circulation. When the TOC-containing water is directly passed through the R0 membrane separation device without biological treatment, the concentration of TOC flowing into the R0 membrane separation device is high, so that it is easy to colonize the RO membrane separation device. In terms of the purpose of inhibiting biofouling in the R0 membrane separation device, it is common to add (2) (2) 1337982 mucilage control agents to the TOC-containing drainage. However, the mucosal control preparation is extremely expensive. Since the drainage discharged from the electronic equipment factory is mixed with the non-ionic surfactant which adheres to the membrane surface of the R0 membrane separation apparatus and has a reduced flow rate, the conventional non-ionic surface activity is contained. The spotted water cannot be separated by R 0 membrane treatment. In addition to the above organic substances, the water discharged from the electronic equipment factory may contain an oxidizing agent such as hydrogen peroxide. When the oxidizing agent is contained in the drainage, the activated carbon column is generally provided in the front stage of the R0 membrane separation apparatus for the purpose of preventing oxidative degradation of the RO membrane by the oxidizing agent. These drainages contain both organic matter, so the activated carbon column is likely to become a hotbed of microorganisms. When the microorganisms multiply in the active tower, the differential pressure of the activated carbon column rises, and the microbial leakage causes the SDI of the activated carbon treated water to rise. SUMMARY OF THE INVENTION The present invention provides a reduction in the amount of flow due to adhesion of a film surface of an organic substance in a membrane separation device during treatment and recovery by the RO membrane separation device, and prevents the biocontamination from being stably treated for a long period of time, thereby effectively reducing TOC concentration in water to obtain high-quality water treatment of organic water treatment methods and devices for the purpose of β
本發明的排水處理方法，具備：在含有機物排水內添 加該含有機物排水中的鈣離子5倍重量以上的氧化皮防止 劑的氧化皮防止劑添加工程；該氧化皮防止劑添加的前、 後或同時在含有機物排水內添加鹼以調整ρ Η爲9,5以上 的ΡΗ調整工程；及將經過該氧化皮防止劑添加工程及pH -5- (3) (3)1337982 調整工程的含有機物排水加以逆滲透膜分離處理的膜分離 工程。 本發明的排水處理裝置，具備：在含有機物排水內添 加該含有機物排水中的鈣離子5倍重量以上的氧化皮防止 劑的氧化皮防止劑添加手段；該氧化皮防止劑添加的前、 後或同時在含有機物排水內添加鹼以調整ρ Η爲9.5以上 的pH調整手段；及導入經過該氧化皮防止劑添加手段及 pH調整手段的含有機物排水的逆滲透膜分離處理裝置。 本發明中，氧化皮防止劑的添加量即使該等氧化皮防 止劑爲鈉鹽等的鹽時，仍是以酸的形式換算的値》 【實施方式】 本發明之一樣態是在導入R0膜分離裝置的被處理水 (以下有稱爲「R0供水」的場合）中添加預定量氧化皮 防止劑的同時調整pH爲9.5以上通過R〇膜分離裝置。 調整R0供水的pH形成9.5以上的理由是如下述。 由於微生物在鹼性域不能生存。因此，藉著將R 0供 水的pH調整爲9.5以上，可以在R0膜分離裝置內形成具 有營養源但微生物不能生存的環境，不需要以往昂貴的黏 膜控制劑的添加，即可抑制R0分離膜裝置的生物污染。 有降低流通量之虞的非離子性表面活性劑會在鹼性區 域中從膜面上脫落附著爲一般所熟知，R 0供水的ρ Η爲 9 · 5以上時，可抑制對R 0膜面之該等成份的附著。 R 〇供水內，添加R 0供水中鈣離子的5倍重量以上氧 -6 - (4) (4)1337982 化皮防止劑的理由是如以下所述。 從電子設備製造工廠等所排出的含TOC排水中有少 數混入形成氧化皮要素的鈣離子等的場合。本發明是將 R0供水的pH形成9.5以上，但是如此之高pH的R0運 轉條件下即使極微量鈣離子的混入仍會生成碳酸鈣等的氧 化皮，而會立即使得R0膜堵塞。本發明從上述因氧化皮 導致膜面堵塞的目的雖於R0供水內添加氧化皮防止劑， 但是該氧化皮防止劑添加量小於鈣離子濃度的5倍量時其 添加效果不足，因此添加蓋離子濃度的5倍量以上。 在此一樣態下，尤其作爲RO膜是以使用].47MPa' 25°C、pH7的條件進行1 500ml/L食鹽水的R0膜分離處理 時的鹽排除率（以下，僅稱爲「鹽排除率」。）具有95% 以上的脫鹽性能的聚乙烯純係的低生物污染用R 0膜進行 R0膜分離處理爲佳。使用上述低生物污染用R0膜的理由 如下。 上述低生物污染用R0膜和通常所使用的芳香族聚醯 胺膜比較，可消除膜表面的載電性，提高親水性，因此具 有非常優異的耐污染性。但是，對於含有多量非離子性表 面活性劑的水會使其耐污染性效果降低，會因時間而降低 流通量。 R 0供水的P Η調整在9 · 5以上時，有降低R 0膜流通 量之虞的非離子性表面活性劑會在膜面上脫落附著，因此 通常所使用的芳香族聚醯胺膜時，可抑制極端之流通量的 降低°但是，R ◦供水中非離子性表面活性劑濃度高的場 (5) (5)1337982 合同樣會降低其效果’長期地使流通量降低。 因此’爲了解決以上的問題，最好是以組合具有上述 特定的脫鹽性能的聚乙烯醇系的低生物污染用R 0膜，和 以R 0供水的ρ Η爲9 · 5以上過水的條件進行，即使針對含 高濃度的非離子性表面活性劑的R 0供水也不致導致流通 量降低可長期間進行穩定的運轉。 爲了更有效地進行處理’以採用下述的條件爲佳。 R0供水的pH以10.5以上，尤其以ι〇·5〜12爲佳。 氧化皮防止劑的添加量以鈣離子濃度的5〜5 0倍量。 RO供水的鈣離子濃度高的場合，進行陽離子交換處 理作爲氧化皮防止劑添加的前處理，除去鈣。 根據此一樣態的排水處理方法及處理裝置，從電子設 備製造工廠、其他各種領域所排出高濃度乃至低濃度含有 機物排水，尤其是使用RO膜分離裝置進行含有非離子性 表面活性劑的排水的處理·回收時，防止R 0膜分離裝置 內因有機物的膜面附著導致流通量的降低、生物污染可長 期進行穩定處理的同時，有效地降低水中TOC濃度獲得 高水質的處理水。以本發明處理所得的處理水可以作爲超 純水製造的原水' 鍋爐用水或者冷卻用水等的使用。 以下參照說明詳細說明一樣態有關之含有機物排水的 處理方法及處理裝置。 第1圖是表示一樣態有關的含有機物排水的處理方法 及處理裝置的系統圖。 第1圖中，在經水槽1導入的原水（含有機物排水） -8- (6)1337982 內，添加氧化皮防止劑之後，添加鹼形成Ρ η 9.5以 後導入R0膜分離裝置進行R0膜分離處理。 添加在原水的氧化皮防止劑雖然可以適當使用 區域解離容易形成金屬離子和配合化合物的乙二胺 (EDTA )或氰基三乙酸（NTA )等螯合物系氧化 劑，但是其他也可以使用（甲基）丙烯酸聚合物及 馬來酸聚合物及其鹽等的低分子量聚合物、乙二胺 磷酸及其鹽、羥基亞乙基二磷酸及其鹽、氰基三甲 及其鹽、磷丁烷三羧酸及其鹽等的磷酸及磷酸鹽、 酸及其鹽、三多磷酸及其鹽等的無機聚合磷酸等。 氧化皮防止劑的添加量爲原水（添加氧化皮防 水）中的耗離子濃度的5倍重量以上。氧化皮防止 加量小於原水中鈣離子濃度的5倍重量時，不能充 氧化皮防止劑的添加效果。氧化劑防止劑即使過度 加在藥劑成本的面並不理想，因此以原水中鈣離子 5〜50倍重量爲佳。 添加氧化皮防止劑的原水，其次添加鹼劑 PH9.5以上’以以上爲佳，最好是10.5〜12 pH 10.5〜11導入RO膜分離裝置2內。在此使用的 氫氧化納、氫氧化鉀等’只要是可以將原水的P Η 9 · 5以上的無機物系鹼劑即可，並無特別的限定u R〇膜分離裝置的RO膜爲具有耐鹼性物，例如 例如聚醯胺酯複合膜 '聚乙烯醇複合膜、芳香族聚 等’但是也可以使用具有1 5〇〇mg/L的食鹽水在1 上，隨 在鹼性 四乙酸 皮防止 其鹽、 四甲撐 基磷酸 六正磷 止劑的 劑的添 分獲得 多量添 濃度的 調整爲 ，例如 鹼劑爲 調整爲 ，可舉 醯胺膜 • 47MPa (7) 1337982 、2 5 °C、ρ Η 7的條件下進行r 〇.膜分離處理時 (以下’僅稱爲「鹽排除率」。）爲9 5 %以上 聚乙烯醇系的低污染用RO膜。使用以上低污 爲佳的理由是如下述。 上述低污染用RO膜和通常所使用的芳香 比較，可消除膜表面的荷電性，提高親水性， 常優異的耐污染性。但是，相對於含有多量的 面活性劑的水會降低其耐污染性，會隨時效使 低。 將RO供水的pH調整爲9.5以上時，有使 通量降低之虞的非離子性表面活性劑會從膜面 著，因此即使使用通常所使用的芳香族聚醯胺 制極端之流通量的降低。但是，RO供水中的 面活性劑濃度高時同樣會降低其效果，長期性 的降低。在RO膜分離裝置的前段進行活性碳 可以藉此減輕因上述表面活性劑導致流通量降 但是持續著長時間處理，仍會使得流通量降低· 組合具有上述脫鹽性能的聚乙烯醇系的低 膜，和RO供水的pH爲9.5以上過水的條件， 於含有高農度的非離子性表面活性劑的R〇供 致流通量的降低可長期間進行穩定的運轉。 RO膜也可以螺旋形、空心系形、管狀形: 式。 RO膜分離裝置2的濃縮水在必要時添加酸 的鹽排除率 脫鹽性能的 染用RO膜 族聚醯胺膜 因此具有非 非離子性表 得流通量降 得RO膜流 產生脫離附 膜時，可抑 非離子性表 導致流通量 處理，雖然 低的問題， 〇 污染用RO 藉此即使對 水時不會導 等任何的型 Μ周整爲p Η -10- (8) (8)1337982 中性之後，排出系統外。並且R ◦膜分離裝置2的滲透水 接著添加酸調整爲PH4〜8，必要時更施以活性碳處理之後 ’再利用或流掉。在此使用的酸尤其沒有限制，可舉例如 鹽酸、零酸等的無機酸。 如第1圖表示，原水中添加預定量的氧化皮防止劑， 同時藉著調整爲pH9.5以上之後進行R0膜分離處理，藉 此不會引起R 〇膜分離裝置之流通量的降低，長期間進行 穩定的處理，獲得高度除去TOC的高水質處理水。 第1圖是表示本發明的一例，本發明並未限定在任何 的圖示中。第]圖是在原水中添加氧化皮防止劑之後，添 加鹼以進行pH調整，但是也可以在原水中添加鹸進行pH 調整之後添加氧化皮防止劑，或者也可以同時進行pH調 整和氧化皮防止劑的添加。利用R0膜分離裝置的處理不 僅限於一段處理，也可以2段以上的多段處理。從電子設 備製造工廠所排出的含TOC排水等基本上混入形成氧化 皮原因的鈣離子等的情形雖少，但是原水中混入鈣離子等 時，也可以設置在氧化皮防止劑添加之前除去鈣離子的陽 離子交換塔，預先除去鈣。也可以設置pH調整或氧化皮 防止劑添加用的混合槽。 〔實施例1〕 以含非離子系表面活性劑的電子設備製造工廠排水（ ΡΗ7·2、TOCIOmg、鈣離子濃度1 m g / L )作爲原水，在原 水內添加二胺四乙酸乙醋酸鈉鹽]〇mg/L作爲氧化皮防止 -11 - (9) (9)1337982 劑之後’添加N a 〇 Η形成pH 1 Ο; 5，以R0膜分離裝置（日 東電工製低壓芳香族聚醯胺型RO膜「NTR-759j )回收 率90%的條件進行R〇膜分離處理。 檢查此時的 R 0膜分離裝置的膜流通量（2 5 t：、 I · 4 7 M p a )和R 〇濃縮水中的生菌數的時效變化，將結果 顯不在第2、3圖。 此外，RO滲透水的TOC濃度爲50#g/L，可以高度 除去TOC。 〔比較例1〕 原水中不添加氧化皮防止劑，使RO供水的pH形成7 之外，並以和實施例1相同條件進行處理，將RO分離膜 分離裝置的膜流通量和RO濃縮水中的生菌數的時效變化 分別表示在第2、3圖中。 〔比較例2〕 原水中不添加氧化皮防止劑，使RO供水的pH形成7 ，在RO供水中添加5mg/L的異噻唑啉系調漿劑（栗田工 業（股）製「夕9 A —夕（商標名）EC- 5 03」）之外以和 實施例1相同條件進行處理，將RO分離膜分離裝置的膜 流通量和生菌數的時效變化分別表示在第2、3圖中。 如第2圖所詳示，實施例1中即使過水開始500hr後 仍不能觀測流通量的降低，相對於此，比較例1在過水開 始3 OOhr後相對於初期流通量即已減少爲一半左右。又， -12- (10) (10)1337982 同樣在添加調漿劑的比較例2中在過水開始3 OOhr及降低 爲初期流通量的60%左右。 又，從第3圖，實施例1及比較例2中，相對於不能 觀測出生菌數的增加，比較例1則隨著過水時間的增加而 同時使得生菌數增加。 從以上的結果，比較例1中由於RO膜內微生物的繁 殖及非離子性表面活性劑的膜面附著的相乘效果使得流通 量降低，比較例2即使藉調漿劑的添加來抑制微生物的繁 殖，仍會因爲非離子性表面活性劑的膜面附著使得流通量 降低，但是本發明的實施例1中明顯地可同時抑制RO膜 分離裝置內的微生物的繁殖及非離子性表面活性劑之膜面 附著的雙方。 〔實施例2 '比較例3〜5〕 RO供水的pH設定爲9_5 (實施例2 ) 、9.2 (比較例 3 ) 、9 (比較例4 )或者8 · 5 (比較例5 )之外，以和實施 例1相同條件進行處理，檢查RO膜分離裝置的膜流通量 的時效變化，將結果表示在第4圖。 第4圖中’ RO供水的pH設定在9.5以上時抑制非離 子表面活性劑的膜面附著及微生物增殖所導致的生物污染 ’獲知可抑制RO膜分離裝置之膜流通量的降低。 〔實施例3、比較例6、7〕 除了氧化皮防止劑的添加量爲5 m g/L (實施例3 )、 -13- (11) (11)1337982 3 m g / L (比較例6 )或者1 m g / L (比較例7 )之外，以和實 施例1相同條件進行處理，檢查R 〇膜分離裝置的膜流通 量的時效變化，將結果表示在第5圖。此外，第5圖中將 氧化皮防止劑的添加量爲1 0 m g / L的實施例1的結果一倂 記入。 第5圖中’氧化皮防止劑的添加量爲鈣離子濃度的5 倍重量以上時，可獲知抑制R ◦膜分離裝置之膜流通量的 降低。此時，調查膜流通量降低的RO膜分離裝置的RO 膜面，可確認附著有碳酸鈣的氧化皮。 〔實施例4〕 以含非離子系表面活性劑的電子設備製造工廠排水（ pH7.2、TOC3 0mg、鈣離子濃度1 m g/L )作爲原水，在原 水內添加二胺四乙酸乙醋酸鈉鹽10mg/L之後，添加NaOH 形成ρΗΙΟ.5，並以RO膜分離裝置（日東電工製聚乙烯醇 系低污染用R Ο膜「L F -1 0」）回收率9 0 %的條件進行R 〇 膜分離處理。 檢查此時的RO膜分離裝置的膜流通量（25°C ' 1.47Mpa) ^將結果顯不在第6圖。 此外，RO滲透水的TOC濃度爲1 00 // g/L，可以高度 除去TOC。 〔實施例5〕 除了使用日東電工製低壓芳香族聚醯胺系膜「 -14 - (12) (12)Γ337982 NTR-7 5 9」作爲R0膜之外，以和實施例4相同條件進行 處理，將RO膜分離裝置的膜流通量的時效變化表示在第 6圖。 〔比較例8〕 除了 RO供水的pH形成7之外，以和實施例4相同 條件進行處理，將R0膜分離裝置的膜流通量的時效變化 表示在第6圖。 如第6圖表示，實施例4中即使過水開始以至大約j 年（SOOhr )之後仍不能觀測出流通量的降低，相對於此 ，實施例5則可確認初期流通量之75 %左右流通量的降牴 。並且，比較例8中流通量降低爲初期流通量的75%左右 。從該結果，以本發明處理非離子性表面活性劑濃度較高 的R0供水時，尤其雖然使用特定的聚乙烯醇系低污染用 R0膜，但是可獲知使超過1 〇〇〇小時的長期流通量的穩定 化極爲有效。 〔實施例6〕 使用丙烯酸系聚合物作爲氧化皮防止劑。 丙烯酸系聚合物的添加量爲lmg/L、3mg/L、5mg/L、 ]〇mg/L。除此之外以和實施例1相同條件進行處理，檢查 RO膜分離裝置的膜流通量的時效變化，將結果顯示在第7 圖6 如第7圖所示，添加供水C a濃度的5倍量以上的丙 -15 - (13)1337982 烯酸系聚合物，獲知可抑制流通量的降低。分析 低的膜表面時，可觀測出碳酸鈣氧化皮的析出。 〔實施例7〕 使用氰基三乙酸（NTA )鈉作爲氧化皮防止| 除了氰基三乙酸鈉系氧化皮防止劑的$ 1.23mg/L、3.7mg/L、6.2mg/L、12.3mg/L (以酸 算時 lmg/L、3mg/L、5mg/L、lOmg/L)以外以和 相同條件進行處理，檢查RO膜分離裝置的膜流 效變化，將結果顯示在第8圖。 如第8圖所示，添加供水C a濃度的5倍量 化皮防止劑的添加量，獲知可抑制流通量的降低 通量降低的膜表面時，可觀測出碳酸鈣氧化皮的1 本發明另一樣態有關的排水處理方法，具備 處理含有機物及氧化劑排水的活性碳處理工程， 活性碳處理工程的該排水施以逆滲透膜分析處理 工程所構成的含有機物及氧化劑排水的處理方法 :在上述活性碳處理工程的更前一階段中，排水 調整pH爲9.5以上的pH調整工程，及在上述膜 更前一階段中，在排水內添加該排水中鈣離子的 以上的氧化皮防止劑的氧化皮防止劑添加工程。 本發明另一樣態有關的排水處理裝置，具備 處理含有機物及氧化劑排水的活性碳處理手段， 活性碳處理手段處理的該排水施以逆滲透膜分析 流通量降 呑加量爲 的形式換 實施例1 通量的時 以上的氧 。分析流 开出。 以活性碳 及將經過 的膜分離 中，具有 中添加鹼 分離工程 5倍重量 以活性碳 及將經過 處理的膜 -16 - (14) (14)1337982 分離手段所構成的含有機物及氧.化劑排水的處理裝置中， 具有：設置在較上述活性碳處理手段更前段，排水中添加 鹼調整pH爲9.5以上的pH調整手段，及設置在較上述膜 分離手段更前段，在排水內添加該排水中鈣離子的5倍重 量以上的氧化皮防止劑的氧化皮防止劑添加手段。 以下，稱供給活性碳處理的被處理水爲「AC供水」 的場合。 該樣態有關的方法及裝置中，將 AC供水調節爲 pH9.5以上，並且供水中添加預定量的氧化皮防止劑的理 由是如下述。 由於微生物不能在鹼性區域不能存活。因此，藉著將 AC供水的pH調節爲9.5以上，可製成雖具有營養源但是 微生物不能存活的環境，可抑制活性碳塔內微生物的繁殖 。從活性碳處理不降低水的pH來看，從該活性塔所流出 的活性碳處理水的pH同樣爲ρΗ9·5以上的鹼性。鹼性的 活性碳處理水供給至R0裝置，在RO膜分離裝置中同樣 可抑制微生物的繁殖，不需要進行如以往昂貴之黏度控制 劑的添加’可以防止R0膜分離裝置的生物污染。 爲了更有效地進行處理，A C的供水的ρ Η以I 0.5以 上爲佳，最好是10.5〜12。 從電子設備製造工廠等所排出的含TO C排水中有混 入些微形成氧化皮要素的鈣離子等的場合。r〇供水的pH 爲9.5以上時’即使極微量的鈣離子仍會生成碳酸鈣等的 氧化皮’使得該氧化皮堵塞R 〇膜。爲了抑制因氧化皮造 -17- (15) (15)1337982 成膜面的堵塞而在R 0供水中添加氧化皮防止劑。該氧化 皮防止劑添加量小於鈣離子濃度的5倍量時’由於其添加 效果不充分，因此以鈣離子濃度的5倍量以上，最好是 5〜5 0倍量。 根據此一樣態的含有機物及氧化劑排水的處理方法及 處理裝置，從電子設備製造工廠、其他各種領域所排出高 濃度乃至含低濃度有機物和氧化劑的排水使用活性碳塔和 RO膜分離裝置進行處理•回收時，可防止RO膜分離裝置 內因有機物的膜面附著導致流通量的降低、活性碳塔及 RO膜分離裝置的生物污染以進行長期的穩定處理，同時 可有效降低水中TOC濃度獲得高水質的處理水。 在此一樣態中，對含有機物及氧化物排水施以活性碳 處理，其次進行RO膜分離處理時，在供給活性碳處理的 AC供水中添加鹼調整爲ρΗ9·5以上，並且在RO膜分離處 理的RO供水中添加預定量的氧化皮防止劑。各處理順序 可舉例以下（I )〜（IV )的樣態。 I )氧化皮防止劑添加—pH調整―活性碳處理->R〇 膜分離處理 Π ) pH調整—氧化皮防止劑添加—活性碳處理—RO 膜分離處理 冚’）pH調整一活性碳處理—氧化皮防止劑添加—RO 膜分離處理 W )氧化皮防止劑添加及p Η調整—活性碳處理—R 0 膜分離處理 -18- (16) (16)1337982 第9圖是以上述（i )的樣態進行處理的系統圖。但 是’此一樣態當然也可以同樣採用上述（Π )或（ΙΠ )或 (IV )的樣態。第9圖是表示活性碳塔作爲活性碳處理手 段’但是活性碳處理手段對於活性碳塔不作任何的限定， 只要使活性碳接觸排水，除去排水中的氧化劑即可。 第9圖中，是在原水（含有機物及氧化劑排水）內添 加氧化皮防止劑之後，過水於活性碳塔11內，將活性碳 處理水經過水槽丨2後導入R0膜分離裝置13進行R0膜 分離處理。 原水內添加氧化皮防止劑的例示是如前述。 氧化皮防止劑的添加量以原水中鈣離子濃度的5-50 倍重量爲佳。其理由如前述。 添加氧化皮防止劑之後的原水接著添加鹼劑調整至 PH9.5以上、以10以上爲佳、最好是10.5〜12 ’例如調整 爲pH 10.5〜1 1導入活性碳塔內。在此使用的鹼劑爲氫氧化 納、氫氧化鉀等’只要可以調整原水的P Η爲9.5以上的 無機物系鹼劑即可’並無特別加以限定。 活性碳塔Π所使用的活性碳種是以可除去椰子殻系 等氧化劑皆可並無特別的限定。又’過水方法同樣可以向 上流、向下流的其中之一，過水sv並未加以限定’但是 以1〜Whr1過水爲佳。 以活性碳塔Η除去氧化劑的活性碳處理水隨後經過 水槽12利用泵Ρ導入RO膜分離裝置13內。R0裝置13 的適當RO膜已如前述。 -19- (17) (17)1337982 R〇膜分離裝置1 3的濃縮.水在必要時添加酸調整爲 PH中性之後’排出系統外。R〇膜分離裝置1 3的滲透水 接著添加酸調整爲pH4〜8 ’必要時更施以活性碳處理等之 後，再利用或放流。在此使用的酸，尤其不加以限制可舉 例如鹽酸、硫酸等的無機酸。 如第9圖表示，原水內添加預定量之氧化皮防止劑的 同時，調整至p Η 9.5以上之後，施以活性碳處理及R 〇膜 分離處理，藉此不致造成RO膜分離裝置之流通量的降低 ’並可以防止活性碳塔及R Ο膜分離裝置的生物污染，長 期間進行穩定的處理，獲得高度除去TOC的高水質處理 水。 第9圖是如前述，表示本發明實施型態的一例，本發 明在不超出其要旨的前提下，並不爲任意的圖示所限定。 第9圖是在供給活性碳塔內的原水內添加氧化皮防止劑之 後，添加鹼進行pH調整，但是也可以在原水內添加鹼進 行P Η調整之後添加氧化皮防止劑，或者也可以同時進行 pH調整和氧化皮防止劑的添加。 此外，也可以在原水內添加鹼進行pH調整之後，供 給至活性碳塔，在活性碳塔流出的水中添加氧化皮防止劑 。使用螯合物系氧化皮防止劑作爲氧化皮防止劑時，雖然 可以添加在上述的任意位置，但是使用低分子量聚合物的 場合會有吸附在活性碳上之虞，因此以添加在活性碳塔流 出的流出水（RO供水）中爲佳。 RO膜分離處理裝置進行的處理不僅限於一段處理’ -20- (18) (18)1337982 也可以進行2段以上的多段處理.。 從電子設備製造工廠所排出的含TOC排水等，基本 上少有混入形成氧化皮原因的鈣離子等情況，但是原水中 混入鈣離子等’在R 〇供水的鈣離子濃度高的場合，也可 以陽離子交換塔進行離子交換處理，以除去鈣。此時，爲 了刪減氧化皮防止劑添加量，以在氧化皮防止劑添加之前 ，進行陽離子交換處理爲佳。也可以設置pH調整或氧化 皮防止劑的添加用的混合槽。 〔實施例8〕 以含有非離子系表面活性劑的電子設備製造工廠排水 CpH7.2、TOClOmg'鈣離子濃度lmg/L、氧化劑（過氧 化氫）含量：3 0 m g/ L )作爲原水，原水中添加二胺四乙酸 乙醋酸鈉鹽1 〇 m g / L作爲氧化皮防止劑之後，添加N a Ο Η 形成ρΗ10.5，以SVIOhr·1過水至活性碳塔（塡充kUraray 製活性碳「KW1 0-32」）內，其活性碳處理水以R〇膜分 離裝置（日東電工製低壓芳香族聚丙烯型R〇膜「NTR-75 9」）在回收率90%的條件下進行RO膜分離處理。 檢查此時的活性碳處理水中的生菌水和RO膜分離裝 置的膜流通量（25°C、1.47Mpa)的時效變化’將結果顯 示於第1 0、1 1圖。 RO滲透水的TOC濃度爲50 g/L ’可以高度除去 TOC。 在原水中不添加N a Ο Η，除了 A C供水的P Η形成7.2 -21 - (19) (19)1337982 以外以和實施例8同樣條件進行處理，將活性碳處理水中 的生菌水和R0膜分離的膜流通量的時效變化分別於第1 0 ' 1 1 圖。 第1 0、1 1圖藉下述得以明確》 從實施例8的活性碳處理水中不能觀測出生菌，相對 於此比較例9的活性碳處理水中可觀測出過水500小時後 已有]04個/mL生菌的漏洩。 實施例8中即使過水開始5 00小時後仍然不能觀測出 流通量的降低，相對於此比較例9從過水開始3 0 0小時雖 然未能觀測出因具有活性碳的有機物吸附作用所導致膜流 通量的降低，但是一旦超過3 00小時後可觀測出有流通量 極端的降低。 〔實施例9、比較例1〇〜12〕 除了 AC供水的pH爲9.5 (實施例9 ) 、9.2 (比較例 10) 、9 (比較例1 1 )或者8 . 5 (比較例1 2 )之外和以實 施例9同樣條件進行處理，檢查RO膜分離裝置的膜流通 量的時效變化，將結果顯示於第】2圖。 從12圖中，AC供水的pH設定爲9.5以上時，RO供 水的pH同樣形成9.5以上，可抑制因非活性表面活性劑 的膜面附著及微生物的增殖導致之生物污染，可抑制RO 膜分離裝置的膜流通量的降低。 〔實施例】0、比較例]3、I 4〕 -22- (20) (20)1337982 除了氧化皮防止劑的添加量.設定爲5mg/L(實施例10 )、3mg/L (比較例1 3 )或者1 mg/L (比較例1 4 )之外和 以實施例1 〇同樣條件進行處理，檢查R 〇膜分離裝置的膜 流通量的時效變化，將結果顯示於第】3圖。並且，在第 1 3圖中一倂記載氧化皮防止劑的添加量設定爲1 0 mg/L的 實施例1的結果。 從1 3圖中，氧化皮防止劑的添加量設定爲鈣離子濃 度的5倍重量以上，可藉以獲知可抑制RO膜分離裝置的 膜流通量的降低。此時，檢查膜流通量降低後的RO膜分 離裝置的RO膜面時，可確認出附著有碳酸鈣的氧化皮。 【圖式簡單說明】 第1圖是表示本發明實施型態的有關含有機物排水處 理方法及處理裝置的系統圖。 第2圖是表示實施例1及比較例1、2的RO膜分離裝 置的膜流通量的時效變化的圖表。 第3圖是表示實施例1及比較例1、2的RO膜分離裝 置的生菌數的時效變化的圖表。 第4圖是表示實施例2及比較例3〜5的RO膜分離裝 置的膜流通量的時效變化的圖表。 第5圖是表示實施例1、3及比較例6、7的RO膜分 離裝置的膜流通量的時效變化的圖表。 第6圖是表示實施例4、5及比較例8的RO膜分離裝 置的膜流通量的時效變化的圖表。 -23 - (21)1337982 第7圖是表示實施例6的結、果的圖表。 第8圖是表示實施例7的結果的圖表。 第9圖是表示本發明其他實施型態的有關含有機物及 氧化劑排水的處理方法及處理裝置的系統圖。 第1 〇圖是表示實施例8及比較例9的活性碳處理水 的生菌數的時效變化的圖表。 第π圖是表示實施例8及比較例9的R0膜分離裝置 的膜流通量的時效變化的圖表。 第12圖是表示實施例9及比較例10〜12的R◦膜分 離裝置的膜流通量的時效變化的圖表。 第〗3圖是表示實施例8、10及比較例13、14的R〇 膜分離裝置的膜流通量的時效變化的圖表。 明 說 符 件 元 要 主 槽 水The wastewater treatment method of the present invention includes: a scale preventing agent addition process for adding a scale inhibitor containing 5 times or more of calcium ions in organic wastewater to the organic wastewater; before and after the addition of the scale inhibitor Or at the same time, adding alkali to the organic matter to adjust the ρ Η to 9,5 or more ΡΗ adjustment project; and the addition of the scale inhibitor and the pH -5- (3) (3) 1337982 Membrane separation engineering for drainage and reverse osmosis membrane separation treatment. The wastewater treatment device according to the present invention includes: a scale inhibitor addition means for adding a scale inhibitor containing 5 times by weight or more of calcium ions in the organic wastewater; and the scale inhibitor is added before and after Or a pH adjustment means in which a base is added to the organic matter drainage to adjust ρ Η to 9.5 or more; and a reverse osmosis membrane separation processing apparatus containing the organic matter drainage by the scale inhibitor addition means and the pH adjustment means is introduced. In the present invention, the amount of the scale inhibitor is such that when the scale inhibitor is a salt such as a sodium salt, it is converted into an acid form. [Embodiment] The same state of the present invention is introduced into the RO film. When a predetermined amount of scale inhibitor is added to the water to be treated (hereinafter referred to as "R0 water supply") in the separation apparatus, the pH is adjusted to 9.5 or more and passed through the R membrane separation apparatus. The reason for adjusting the pH of the R0 water supply to 9.5 or more is as follows. Because microorganisms cannot survive in the alkaline domain. Therefore, by adjusting the pH of the R 0 water supply to 9.5 or more, an environment having a nutrient source but no microorganisms can be formed in the R0 membrane separation device, and the R0 separation membrane can be suppressed without the addition of an expensive mucous membrane control agent. Biological contamination of the device. It is generally known that a nonionic surfactant having a reduced flow rate is detached from the film surface in an alkaline region, and when the ρ 供水 of the R 0 water supply is 9.5 or more, the surface of the R 0 film can be suppressed. The attachment of such components. In the R 〇 water supply, 5 times or more of the calcium ion in the R 0 water supply is added. The reason for the -6 - (4) (4) 1337982 skin agent is as follows. When there is a small amount of TOC-containing wastewater discharged from an electronic equipment manufacturing plant or the like, calcium ions or the like which form a scale element are mixed. In the present invention, the pH of the R0 water supply is formed to be 9.5 or more. However, even if a very small amount of calcium ions are mixed in the R0 operating condition of such a high pH, an oxide skin such as calcium carbonate is formed, and the R0 film is immediately clogged. In the present invention, the scale preventing agent is added to the R0 water supply for the purpose of clogging the film surface due to the scale. However, when the amount of the scale inhibitor is less than 5 times the calcium ion concentration, the effect of addition is insufficient, so that the cap ion is added. More than 5 times the concentration. In this same state, in particular, the RO membrane is a salt removal rate when the R0 membrane separation treatment of 1 500 ml/L saline is carried out under the conditions of .47 MPa' 25 ° C and pH 7 (hereinafter, simply referred to as "salt elimination". The rate of "lower biocontamination of polyethylene pure system having a desalting performance of 95% or more is preferably carried out by R0 membrane separation treatment using an R 0 membrane. The reason for using the above R0 film for low biocontamination is as follows. The R0 film for low biocontamination described above has a very excellent anti-pollution property as compared with the commonly used aromatic polyamide film, which can eliminate the chargeability on the surface of the film and improve the hydrophilicity. However, water containing a large amount of nonionic surfactant lowers the stain resistance effect and reduces the amount of flow due to time. When the P 供水 of the R 0 water supply is adjusted to 9.5 or more, the nonionic surfactant which reduces the flow of the R 0 film will fall off and adhere to the film surface. Therefore, when the aromatic polyimide film is usually used, It can suppress the decrease in the extreme flow rate. However, the field where the concentration of the nonionic surfactant in the R ◦ water supply is high (5) (5) 1337982 is also reduced, and the flow rate is lowered for a long period of time. Therefore, in order to solve the above problems, it is preferable to combine a polyvinyl alcohol-based low biocontamination R 0 film having the above specific desalting performance, and a ρ 供水 water supply of R 0 to be 9.5 or more. Even if the water supply to the R 0 containing a high concentration of the nonionic surfactant does not cause a decrease in the flow rate, stable operation can be performed for a long period of time. In order to carry out the treatment more efficiently, it is preferable to adopt the following conditions. The pH of the R0 water supply is 10.5 or more, particularly preferably ι〇5~12. The amount of the scale inhibitor is added in an amount of 5 to 50 times the calcium ion concentration. When the calcium ion concentration of the RO water supply is high, the cation exchange treatment is carried out as a pretreatment for the addition of the scale inhibitor to remove calcium. According to the drainage treatment method and the treatment apparatus of the same state, high-concentration or low-concentration discharge of organic matter is discharged from an electronic equipment manufacturing factory and various other fields, and in particular, drainage using a non-ionic surfactant is performed using an RO membrane separation device. During the treatment and recovery, it is possible to prevent the flow rate from being lowered due to the adhesion of the organic film on the membrane surface of the R 0 membrane separation device, and the bio-contamination can be stably treated for a long period of time, and the TOC concentration in the water can be effectively reduced to obtain treated water having high water quality. The treated water obtained by the treatment of the present invention can be used as raw water produced by ultrapure water, boiler water or cooling water. Hereinafter, a treatment method and a treatment apparatus containing organic matter drainage in the same state will be described in detail with reference to the description. Fig. 1 is a system diagram showing a processing method and a processing apparatus containing organic matter drainage in the same state. In the first figure, after the scale inhibitor is added to the raw water (containing the organic matter drain) -8-(6)1337982 introduced through the water tank 1, the alkali is added to form Ρ 9.5 and then introduced into the R0 membrane separation device for the R0 membrane separation treatment. . The oxide scale inhibitor added to the raw water may be used as a chelating agent such as ethylenediamine (EDTA) or cyanotriacetic acid (NTA), which is easily dissociated from the metal ion and the compound, but may be used. Low molecular weight polymer such as acrylic acid polymer and maleic acid polymer and its salt, ethylenediamine phosphate and its salt, hydroxyethylidene diphosphate and its salt, cyanotrimethyl and its salt, phosphorus butane III A phosphoric acid such as a carboxylic acid or a salt thereof, an inorganic polymerized phosphoric acid such as a phosphate, an acid or a salt thereof, a tripolyphosphoric acid or a salt thereof, or the like. The amount of the scale inhibitor to be added is 5 times or more by weight of the ion in the raw water (addition of scale to prevent water). When the scale is prevented from being less than 5 times the weight of the calcium ion in the raw water, the effect of adding the scale inhibitor cannot be obtained. The oxidizing agent preventing agent is not preferable because it is excessively added to the cost of the drug, and therefore it is preferably 5 to 50 times the weight of the calcium ion in the raw water. The raw water to which the scale inhibitor is added is added to the RO membrane separation device 2 in order to add the alkali agent PH 9.5 or more, preferably at least 10.5 to 12 pH 10.5 to 11. The sodium hydroxide, potassium hydroxide, and the like used herein may be an inorganic base agent which can be used as a raw material of P Η 5.9 or more, and the RO membrane of the U R membrane separation apparatus is not particularly limited. A basic substance such as, for example, a polyurethane composite film 'polyvinyl alcohol composite film, aromatic poly, etc.' but it is also possible to use a saline solution having 15 μg/L on 1, followed by alkaline tetraacetate The concentration of the agent for preventing the salt or the tetramethylphosphoric acid hexaphosphorus phosphate is adjusted to a large amount, for example, the alkali agent is adjusted to be an amine film. 47 MPa (7) 1337982, 25 ° C In the case of ρ 〇 7 , the membrane separation treatment (hereinafter referred to as "salt elimination rate") is a low-contamination RO membrane of 95% or more. The reason for using the above low pollution is as follows. The RO film for low pollution described above can eliminate the chargeability of the surface of the film, improve the hydrophilicity, and often have excellent stain resistance as compared with the commonly used aroma. However, water with a large amount of surfactant reduces the stain resistance and is less effective at any time. When the pH of the RO water supply is adjusted to 9.5 or more, the nonionic surfactant which lowers the flux is exposed from the film, and therefore the amount of extreme flow of the aromatic polyamine which is usually used is lowered. . However, when the concentration of the surfactant in the RO water supply is high, the effect is also lowered, and the long-term decrease is caused. By performing activated carbon in the front stage of the RO membrane separation apparatus, it is possible to reduce the flow rate due to the above-mentioned surfactant, but the treatment is continued for a long period of time, and the flow rate is still lowered. The polyvinyl alcohol-based low film having the above-mentioned desalination performance is combined. And the pH of the RO water supply is 9.5 or more, and the stable operation can be performed for a long period of time when the R 〇 supply amount of the nonionic surfactant containing a high agricultural degree is lowered. The RO film can also be spiral, hollow, or tubular: When the concentrated water of the RO membrane separation device 2 is added with an acid salt removal rate, if necessary, the RO membrane group polyamide membrane is dyed, so that the non-nonionic surface flow is reduced and the RO membrane flow is released from the attached film. The non-ionic table can be used to cause liquidity treatment. Although the problem is low, the pollution is reduced by RO, so that even if it is not water, it will not be converted into any type of p Η -10- (8) (8) 1337982. After the sex, it is discharged outside the system. Further, the permeated water of the R diaphragm separation device 2 is adjusted to have a pH of 4 to 8 and, if necessary, subjected to activated carbon treatment, and then reused or discharged. The acid to be used herein is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid and zero acid. As shown in Fig. 1, a predetermined amount of the scale inhibitor is added to the raw water, and the R0 membrane separation treatment is carried out by adjusting to pH 9.5 or more, thereby preventing the flow of the R membrane separation device from being lowered. Stable treatment is carried out during this period to obtain high-quality water with high TOC removal. Fig. 1 is a view showing an example of the present invention, and the present invention is not limited to any of the drawings. The figure is a method of adding a base to adjust the pH after adding a scale inhibitor to raw water. However, it is also possible to add a scale to the raw water to adjust the pH, and then add a scale inhibitor, or to adjust the pH and the scale inhibitor simultaneously. Add to. The treatment by the R0 membrane separation apparatus is not limited to one-stage treatment, and may be multi-stage treatment of two or more stages. Although it is rare to contain calcium ions or the like which are caused by the formation of scales, such as TOC drainage, which is discharged from an electronic equipment manufacturing plant, when calcium ions or the like are mixed in the raw water, it is also possible to remove calcium ions before the addition of the scale inhibitor. The cation exchange column removes calcium in advance. It is also possible to provide a mixing tank for pH adjustment or scale inhibitor addition. [Example 1] A factory wastewater (ΡΗ7.2, 2, TOCIOmg, calcium ion concentration 1 mg / L) was used as a raw water in an electronic equipment containing a nonionic surfactant, and sodium diaminetetraacetate ethyl acetate was added to the raw water. 〇mg/L as oxide scale prevention -11 - (9) (9)1337982 After the addition of 'N a 〇Η to form pH 1 Ο; 5, with R0 membrane separation device (Nitto Electric made low pressure aromatic polyamine type RO The membrane "NTR-759j" was subjected to R 〇 membrane separation treatment under the condition of 90% recovery. The membrane flux of the R 0 membrane separation device at this time (2 5 t:, I · 4 7 M pa ) and R 〇 concentrated water were examined. The aging change of the number of bacteria was not shown in Figures 2 and 3. In addition, the TOC concentration of the RO permeate water was 50 #g/L, and the TOC was highly removed. [Comparative Example 1] No scale was added to the raw water. The agent was treated with the same conditions as in Example 1 except that the pH of the RO water supply was 7, and the aging change of the membrane flux of the RO separation membrane separation device and the number of bacteria in the RO concentrated water was shown in the second. (3) [Comparative Example 2] No oxide scale inhibitor was added to the raw water to form the pH of the RO water supply. In addition to the same conditions as in Example 1, except that 5 mg/L of an isothiazoline-based slurry was added to the RO water supply ("9 9 A-night (trade name) EC-503" manufactured by Kurita Industrial Co., Ltd.). The treatment and the aging change of the membrane flux and the number of bacteria in the RO separation membrane separation device are shown in Figs. 2 and 3, respectively. As shown in Fig. 2, in Example 1, even if the water flow was not started for 500 hr, the decrease in the amount of flow was not observed. On the other hand, in Comparative Example 1, the amount of the first flow was reduced to half after the start of the water supply for 300 hr. about. Further, -12-(10) (10)1337982 In the same manner as in Comparative Example 2 in which the slurry was added, the water began to be dried for 3 00 hr and decreased to about 60% of the initial flow rate. Further, from Fig. 3, in Example 1 and Comparative Example 2, Comparative Example 1 increased the number of bacteria at the same time as the water passage time increased with respect to the increase in the number of birthable bacteria that could not be observed. From the above results, in Comparative Example 1, the multiplication effect of the microorganisms in the RO membrane and the membrane surface adhesion of the nonionic surfactant reduced the flow rate, and Comparative Example 2 inhibited the microorganisms even by the addition of the slurry. Propagation, the flow rate is still lowered by the membrane surface adhesion of the nonionic surfactant, but in the first embodiment of the present invention, it is apparent that the growth of microorganisms in the RO membrane separation device and the nonionic surfactant can be simultaneously suppressed. Both sides of the membrane surface are attached. [Example 2 'Comparative Examples 3 to 5] The pH of the RO water supply was set to 9_5 (Example 2), 9.2 (Comparative Example 3), 9 (Comparative Example 4) or 8·5 (Comparative Example 5), The treatment was carried out under the same conditions as in Example 1 to examine the aging change of the membrane flux of the RO membrane separation apparatus, and the results are shown in Fig. 4. In Fig. 4, when the pH of the RO water supply is set to 9.5 or more, the membrane surface adhesion of the non-ionic surfactant and the biofouling caused by the microbial growth are suppressed. It is known that the decrease in the membrane flow rate of the RO membrane separation device can be suppressed. [Example 3, Comparative Examples 6, 7] The addition amount of the scale inhibitor was 5 mg/L (Example 3), -13-(11) (11) 1337982 3 mg / L (Comparative Example 6) or The treatment was carried out under the same conditions as in Example 1 except for 1 mg / L (Comparative Example 7), and the aging change of the membrane flux of the R ruthenium membrane separation apparatus was examined, and the results are shown in Fig. 5. Further, in Fig. 5, the results of Example 1 in which the amount of the scale inhibitor was added was 10 m / L were recorded. When the amount of the scale inhibitor to be added is 5 times or more by weight of the calcium ion concentration in Fig. 5, it is known that the decrease in the film throughput of the R membrane separation apparatus is suppressed. At this time, the RO membrane surface of the RO membrane separation apparatus having a reduced membrane flux was examined, and the scale to which calcium carbonate adhered was confirmed. [Example 4] A factory water supply (pH 7.2, TOC3 0 mg, calcium ion concentration: 1 mg/L) was used as a raw water in an electronic equipment containing a nonionic surfactant, and sodium diaminetetraacetic acid ethyl acetate was added to the raw water. After 10 mg/L, NaOH was added to form ρΗΙΟ.5, and the R film was prepared under the conditions of a recovery rate of 90% by the RO membrane separation apparatus (R-ruthenium film "LF-1O" for polyvinyl alcohol-based low-contamination of Nitto Denko). Separation process. The membrane flux of the RO membrane separation device at this time (25 ° C ' 1.47 MPa) was examined. The results are not shown in Fig. 6. In addition, the RO permeate water has a TOC concentration of 100 // g/L, which can remove TOC highly. [Example 5] The treatment was carried out under the same conditions as in Example 4 except that the low-pressure aromatic polyamide film "-14 - (12) (12) Γ 337982 NTR-7 5 9" manufactured by Nitto Denko Corporation was used as the R0 film. The aging change of the membrane flux of the RO membrane separation device is shown in Fig. 6. [Comparative Example 8] The treatment was carried out under the same conditions as in Example 4 except that the pH of the RO water supply was 7, and the aging change of the membrane flux of the RO membrane separation apparatus was shown in Fig. 6. As shown in Fig. 6, in Example 4, even if the water was started until about 100 years (SOOhr), the decrease in the amount of flow was not observed. On the other hand, in Example 5, the flow rate of about 75% of the initial flow rate was confirmed. The hail. Further, in Comparative Example 8, the flow rate was reduced to about 75% of the initial flow rate. From this result, in the case of treating the R0 water supply having a high concentration of the nonionic surfactant in the present invention, in particular, although a specific polyvinyl alcohol-based low-pollution R0 film is used, it is known that the long-term circulation of more than 1 hour is obtained. The stabilization of the amount is extremely effective. [Example 6] An acrylic polymer was used as a scale inhibitor. The amount of the acrylic polymer added was 1 mg/L, 3 mg/L, 5 mg/L, and 〇mg/L. Otherwise, the treatment was carried out under the same conditions as in Example 1, and the aging change of the membrane flux of the RO membrane separation device was examined. The results are shown in Fig. 7 and Fig. 7 as shown in Fig. 7, and the concentration of the water supply C a was added five times. The amount of the C-15-(13)1337982 enoic acid-based polymer is more than that, and it is known that the decrease in the amount of flow can be suppressed. When the surface of the film was analyzed, the precipitation of the scale of the calcium carbonate was observed. [Example 7] Use of sodium cyanotriacetic acid (NTA) as a scale prevention | Except for the sodium cyanide triacetate scale inhibitor, 1.23 mg/L, 3.7 mg/L, 6.2 mg/L, 12.3 mg/ L (other than lmg/L, 3 mg/L, 5 mg/L, lOmg/L) was treated under the same conditions, and the membrane fluidity change of the RO membrane separation device was examined, and the results are shown in Fig. 8. As shown in Fig. 8, the amount of addition of the skin anti-seeding agent is increased by 5 times the concentration of the water supply C a , and when the film surface having a reduced flux reduction is known, it is possible to observe the scale of the calcium carbonate oxide. The same state of the drainage treatment method, which has an activated carbon treatment process for treating organic matter and oxidant drainage, and the treatment method of the reverse osmosis membrane analysis and treatment project for the activated carbon treatment project includes a treatment method containing organic matter and oxidant drainage: In the previous stage of the activated carbon treatment project, the pH adjustment project in which the drainage adjustment pH is 9.5 or more, and the oxidation prevention agent in which the calcium ions in the drainage are added to the drainage in the previous stage of the membrane are oxidized. Skin anti-blocking agent added to the project. A wastewater treatment apparatus according to another aspect of the present invention includes an activated carbon treatment means for treating a discharge containing an organic matter and an oxidant, and the wastewater treated by the activated carbon treatment means is subjected to a reverse osmosis membrane to analyze a flow rate reduction amount. 1 The amount of oxygen above the flux. Analytical flow opens. In the separation of activated carbon and the membrane to be passed through, there is an organic matter and oxygenation of 5 times the weight of the activated alkali separation process and the treated membrane-16 - (14) (14) 1337982 separation means. The treatment device for the drainage of the agent has a pH adjustment means provided in a stage earlier than the activated carbon treatment means, and a pH adjustment of the alkali is adjusted to 9.5 or more in the drainage, and is provided in the lower stage than the membrane separation means, and is added in the drainage A means for adding a scale inhibitor to a scale inhibitor of 5 times by weight or more of calcium ions in the drainage. Hereinafter, the case where the treated water to be subjected to the activated carbon treatment is referred to as "AC water supply" will be referred to. In the method and apparatus according to this aspect, the AC water supply is adjusted to pH 9.5 or more, and the reason for adding a predetermined amount of scale inhibitor to the water supply is as follows. Because microorganisms cannot survive in alkaline areas. Therefore, by adjusting the pH of the AC water supply to 9.5 or more, it is possible to produce an environment in which the microorganisms cannot survive despite the nutrient source, and the growth of microorganisms in the activated carbon column can be suppressed. The pH of the activated carbon-treated water flowing out of the active tower is also alkaline at a pH of not more than 9.5, from the viewpoint of the activated carbon treatment not lowering the pH of the water. The alkaline activated carbon treatment water is supplied to the RO unit, and the growth of microorganisms can be suppressed in the RO membrane separation apparatus as well, and the addition of an expensive viscosity control agent as in the prior art is not required to prevent biofouling of the RO membrane separation device. For more efficient treatment, the water supply of A C has a ρ Η of preferably I 0.5 or more, preferably 10.5 to 12. When the TO C-containing water discharged from an electronic equipment manufacturing plant or the like is mixed with calcium ions or the like which are slightly formed into scale elements. When the pH of the r〇 water supply is 9.5 or more, even if a very small amount of calcium ions generate an oxide scale such as calcium carbonate, the scale occludes the R ruthenium film. In order to suppress clogging of the film formation surface by the oxide scale -17-(15) (15) 1337982, a scale inhibitor is added to the R 0 water supply. When the amount of the scale inhibitor is less than 5 times the calcium ion concentration, the addition effect is insufficient, so that the calcium ion concentration is 5 times or more, preferably 5 to 50 times. According to the same method and apparatus for treating organic matter and oxidant drainage, the high-concentration and even the low-concentration organic matter and oxidant discharged from the electronic equipment manufacturing plant and various other fields are treated with an activated carbon column and an RO membrane separation device. • When recycling, it can prevent the flow of the organic membrane due to the adhesion of the membrane surface of the RO membrane separation device, the biological contamination of the activated carbon column and the RO membrane separation device for long-term stable treatment, and at the same time effectively reduce the TOC concentration in the water to obtain high water quality. Treatment of water. In this same state, the activated carbon treatment is carried out on the organic matter and the oxide drainage, and when the RO membrane separation treatment is performed, the alkali is added to the AC water supply to which the activated carbon treatment is supplied, and the alkali is adjusted to ρΗ9·5 or more, and the RO membrane is separated. A predetermined amount of scale inhibitor is added to the treated RO water supply. The order of each processing can be exemplified by the following (I) to (IV). I) Oxide prevention agent addition - pH adjustment - activated carbon treatment - > R membrane separation treatment Π ) pH adjustment - oxide scale inhibitor addition - activated carbon treatment - RO membrane separation treatment 冚 ') pH adjustment - activated carbon treatment - Anti-oxidation agent addition - RO membrane separation treatment W) Oxide prevention agent addition and p Η adjustment - activated carbon treatment - R 0 membrane separation treatment -18- (16) (16) 1337982 Figure 9 is the above (i System diagram for processing. However, it is of course also possible to adopt the above (Π) or (ΙΠ) or (IV). Fig. 9 is a view showing the activated carbon column as an activated carbon treatment step. However, the activated carbon treatment means does not limit the activated carbon column, and the activated carbon may be contacted with water to remove the oxidizing agent in the drainage. In Fig. 9, after the scale inhibitor is added to the raw water (containing the organic matter and the oxidant drainage), the activated carbon treated water is passed through the water tank 丨2 and then introduced into the R0 membrane separation device 13 for R0. Membrane separation treatment. An example in which the scale inhibitor is added to the raw water is as described above. The amount of the scale inhibitor is preferably 5 to 50 times the weight of the calcium ion in the raw water. The reason is as described above. The raw water after the addition of the scale inhibitor is adjusted to pH 9.5 or higher, preferably 10 or more, preferably 10.5 to 12 Å, for example, adjusted to pH 10.5 to 1 1 to be introduced into the activated carbon column. The alkali agent to be used herein is not particularly limited as long as it can adjust the inorganic hydrazine having a P Η of 9.5 or more in the raw water. The activated carbon used in the activated carbon column is not particularly limited as long as it is an oxidizing agent such as a coconut shell. In addition, the water passing method can also be one of the upflow and the downflow, and the water sv is not limited', but it is preferable to use water of 1 to Whr1. The activated carbon treated water from which the oxidizing agent is removed by the activated carbon column is then introduced into the RO membrane separating device 13 through the water tank 12 by means of a pump. The appropriate RO film of the R0 device 13 has been as described above. -19- (17) (17) 1337982 R Concentration of the membrane separation device 1 3. Water is added to the pH neutral after the addition of acid, and is discharged outside the system. The permeated water of the R membrane separation apparatus 13 is adjusted to pH 4 to 8 by the addition of acid. If necessary, it is subjected to activated carbon treatment or the like, and then reused or discharged. The acid to be used herein is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid and sulfuric acid. As shown in Fig. 9, when a predetermined amount of the scale inhibitor is added to the raw water and adjusted to p Η 9.5 or more, the activated carbon treatment and the R membrane separation treatment are applied, thereby preventing the flow of the RO membrane separation device. The reduction of 'can prevent bio-contamination of the activated carbon column and the R diaphragm separation device, and the stable treatment is carried out for a long period of time, and high-quality water treatment water with high TOC removal is obtained. Fig. 9 is a view showing an embodiment of the present invention as described above, and the present invention is not limited to any of the drawings without departing from the gist of the invention. In the ninth aspect, after the scale inhibitor is added to the raw water supplied to the activated carbon column, the pH is adjusted by adding an alkali. However, the base may be added to the raw water to adjust the P Η and then the scale inhibitor may be added, or the scale inhibitor may be added simultaneously. pH adjustment and addition of scale inhibitor. Further, a base may be added to the raw water for pH adjustment, and then supplied to the activated carbon column, and a scale inhibitor may be added to the water flowing out of the activated carbon column. When a chelate-based scale inhibitor is used as the scale inhibitor, it may be added to any of the above-mentioned positions. However, when a low-molecular-weight polymer is used, it may be adsorbed on the activated carbon, so that it is added to the activated carbon column. It is preferable to flow out of the effluent water (RO water supply). The processing by the RO membrane separation processing apparatus is not limited to one section of processing -20-(18) (18) 1337982, and it is also possible to perform multi-stage processing of two or more stages. In the case of TOC-containing water discharged from an electronic equipment manufacturing plant, there are basically few calcium ions mixed into the cause of scale formation, but calcium ions are mixed in raw water, etc. When the concentration of calcium ions in the R 〇 water supply is high, The cation exchange column is subjected to an ion exchange treatment to remove calcium. At this time, in order to reduce the amount of the scale inhibitor added, it is preferred to carry out the cation exchange treatment before the addition of the scale inhibitor. It is also possible to provide a mixing tank for pH adjustment or addition of an oxidizing agent. [Example 8] A plant wastewater CpH7.2, a TOClOmg' calcium ion concentration of 1 mg/L, and an oxidizing agent (hydrogen peroxide content: 30 mg/L) were used as raw water in an electronic equipment containing a nonionic surfactant. After adding 1 〇mg / L of diaminetetraacetic acid sodium acetate to the water as a scale inhibitor, add Na a Ο Η to form ρΗ10.5, and pass SVIOhr·1 to the activated carbon tower (additional kUraray activated carbon) In the KW1 0-32"), the activated carbon treated water is subjected to an RO membrane at a recovery rate of 90% using an R membrane separation apparatus (Nitto Electric's low-pressure aromatic polypropylene type R〇 film "NTR-75 9"). Separation process. The aging change of the membrane flux (25 ° C, 1.47 MPa) of the slurry water and the RO membrane separation device in the activated carbon treated water at this time was examined, and the results are shown in Figures 1 and 11. The TOC concentration of RO permeate water is 50 g/L' to remove TOC highly. No Na a Ο 添加 was added to the raw water, except that the P Η of the AC water supply was formed 7.2 -21 - (19) (19) 1337982, and the same conditions as in Example 8 were carried out to treat the bacterial water and the R0 film in the activated carbon treated water. The aging change of the separated membrane flux is shown in Fig. 1 0 '1 1 . It is clear from the following figure 10 and 1 1 that the birth bacteria could not be observed from the activated carbon treated water of Example 8, and it was observed that the activated carbon treated water of Comparative Example 9 was observed after 500 hours of water. Leakage of /mL bacteria. In Example 8, even after 500 hours from the start of the water, the decrease in the amount of the liquid could not be observed. In contrast, in Comparative Example 9, the adsorption of the organic substance having activated carbon was not observed even after 300 hours from the start of the water. The membrane flux is reduced, but once more than 300 hours have passed, an extreme decrease in throughput can be observed. [Example 9 and Comparative Examples 1 to 12] The pH of the AC water supply was 9.5 (Example 9), 9.2 (Comparative Example 10), 9 (Comparative Example 1 1) or 8.5 (Comparative Example 1 2). The treatment was carried out under the same conditions as in Example 9 to examine the aging change of the membrane flux of the RO membrane separation apparatus, and the results are shown in Fig. 2 . When the pH of the AC water supply is set to 9.5 or more, the pH of the RO water supply is also 9.5 or more, which suppresses biofouling due to adhesion of the surface of the inactive surfactant and proliferation of microorganisms, and suppresses RO membrane separation. The membrane throughput of the device is reduced. [Examples] 0, Comparative Example] 3, I 4] -22- (20) (20) 1339982 In addition to the addition amount of the scale inhibitor, it was set to 5 mg/L (Example 10) and 3 mg/L (Comparative Example) 1 3 ) or 1 mg/L (Comparative Example 14) was treated in the same manner as in Example 1 ,, and the aging change of the membrane flux of the R ruthenium membrane separation device was examined, and the results are shown in Fig. 3 . Further, in Fig. 3, the results of Example 1 in which the amount of the scale inhibitor was added was set to 10 mg/L. In the Fig. 3, the amount of the scale inhibitor is set to be 5 times or more by weight of the calcium ion, and it can be understood that the decrease in the membrane flux of the RO membrane separator can be suppressed. At this time, when the RO membrane surface of the RO membrane separation device after the membrane flow rate was lowered was examined, it was confirmed that the scale of the calcium carbonate adhered. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a system diagram showing a method and a processing apparatus for containing organic matter in accordance with an embodiment of the present invention. Fig. 2 is a graph showing the aging change of the film flow amount of the RO membrane separation device of Example 1 and Comparative Examples 1 and 2. Fig. 3 is a graph showing the aging change of the number of bacteria in the RO membrane separation device of Example 1 and Comparative Examples 1 and 2. Fig. 4 is a graph showing the aging change of the film flow amount of the RO membrane separation device of Example 2 and Comparative Examples 3 to 5. Fig. 5 is a graph showing the aging change of the film throughput of the RO membrane separation apparatuses of Examples 1 and 3 and Comparative Examples 6 and 7. Fig. 6 is a graph showing the aging change of the film throughput of the RO membrane separation devices of Examples 4 and 5 and Comparative Example 8. -23 - (21) 1337982 Figure 7 is a graph showing the knot and fruit of Example 6. Fig. 8 is a graph showing the results of Example 7. Fig. 9 is a system diagram showing a processing method and a processing apparatus for containing organic matter and oxidant drainage according to another embodiment of the present invention. Fig. 1 is a graph showing the aging change in the number of bacteria in the activated carbon-treated water of Example 8 and Comparative Example 9. The πth diagram is a graph showing the aging change of the film throughput of the RO membrane separation apparatus of Example 8 and Comparative Example 9. Fig. 12 is a graph showing the aging change of the film throughput of the R ◦ membrane separation apparatus of Example 9 and Comparative Examples 10 to 12. Fig. 3 is a graph showing the aging change of the film throughput of the R 膜 membrane separation apparatuses of Examples 8 and 10 and Comparative Examples 13 and 14. Ming said that the symbol element is the main slot water
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