574144 Α7 Β7 五、發明説明（1 ) 相關申請案 2 3 5 ，9 9 2 號係 茲將其中所述者列入 (請先閲讀背面之注意事項再填寫本頁) 相關之暫定專利申請案第6 0 於2〇00年9月26日提出申請 參考。 發明範園 本發明一般係關於廢水處理。更特定言之，本發明提 出處理工業廢水以藉由氨之化學破壞、以幾近化學計量的 鈣鹽處理和過濾而連續移除氨和氟化物改良系統和更有效 的方法。 發明背景 經 濟 部 智 慧 財 產 β) 員 X 消 費 合 作 社 印 製 業中以加工砂石晶 度氟化銨或二氟化 至自來水系統之前 排放限制可能低於 氨’氨的排放限制 鈣之沉澱，使得處 放限制，發展出多 中之氨濃度的方法 ’且，欲達到極低 進行。此消耗大量 無固體時進行。此 緩衝的氧化物蝕刻法用於半導體工 片。此緩衝的氧化物蝕刻法須使用高濃 銨，其最後留在半導體廢水中。在排放 ，必須移除廢水流中的氟化物，且地域 5 p p m。通常也必須先移除廢水中的 可能低至5 p p m。此外，氨干擾氟化 理程序必須使用大量過量的鈣鹽。 爲符合廢水中的氨和/或氟化物排 種處理方法。空氣滌氣是一種降低廢水 。空氣滌氣必須於提高的鹼性p Η進行 氨濃度時，在ρ Η大於1 〇的熱溶液中 能量，須添加大量鹼，且必須於廢水中 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -4- 574144 B7 五、發明説明（2 ) (請先閲讀背面之注意事項再填寫本頁) 外，以化學方式破壞氨以外’此方法會將其轉變成氣相， 必須將其滌入酸性吸收溶液中或者排放至環境中。氟化物 不易以空氣滌除，因此必須在空氣滌氣之前或之後於獨立 步驟中移除。 逆滲透（R〇）是另一可用以處理氟化物和氨的廢水 處理技巧。但是，R〇因爲形成鱗狀物或在濾膜上有生物 生長，所以對膜污染敏感。在過瀘步驟之前移除鈣、鎂和 其他形成鱗狀物的物質，或者更常是將廢水予以酸化以制 止碳酸鈣和鎂之沉澱.，或者藉由添加分散劑以阻礙R〇膜 表面之髒污，得以避免鱗狀物形成。也必須移除溶劑（如 ••醇或酮）和其他化學或生物氧需求物，以免在生物生長 於膜上。經酸化的R ◦濃縮物優先含有氨和氟化物，但以 空氣滌氣時，氨不會被化學方式破壞。通常在R〇濃縮步 驟之後移除氟化物。但是，濃縮物中的氨濃度提高會阻礙 氟化鈣沉澱，此時須使用大量過量的鈣鹽。 經濟部智慧財產局員工消費合作社印製 另一處理技術是使用陽離子交換樹脂的離子交換。但 是，因爲樹脂必須經再生處理，此通常使得化學成本高， 所以此方法在用於氨濃度高的廢水方面效果不大。至於使 用前面所討論的方法，氨幾乎完全自廢水移至不同介質（ 此處爲濃縮的酸廢液流）中。爲避免氨的自身滌除，必須 密切偵測和調整通入的廢水之p Η和濃度。其他陽離子（ 如：15、鎂、鈉之類）會干擾氨之移除。因爲形成緩衝的 氟化銨化合物，所以氟化物會干擾氨的有效移除；氨會干 擾氟化物沉澱。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） " " _5_ 574144 B7 五、發明説明（3 ) (請先閲讀背面之注意事項再填寫本頁) 生物處理曾被用以破壞廢水中的氨。但這樣的處理緩 慢且相當無效，須建構成本和空間需求相當大的處理槽’ 其對於溫度和離子強度及存在於廢水中的其他化合物敏感 且須要有機物和肥料輔助。因爲只有低含量氟化物與生物 處理可相配伍，所以必須稀釋此廢水。因爲氟化鈣溶解度 (約1 6 p P m )造成的限制，所以在處理廢水之前稀釋 及抑制氟化物沉澱。因此，無論初時的氟化物濃度如何’ 因爲沉澱而達到類似的氟化物流出濃度，此使得處理法排 出的氟化物總量隨稀釋而提高。這是處理高濃度氟化物的 效果優於處理低濃度氟化物的原因。 也曾以次氯酸鹽化學破壞而移除氨，但效果有限。有 機物存在會形成鹵化的有機化合物。殘留的次氯酸鹽如果 與未反應的氨溶液混合（例如，經處理的廢水與其他未經 處理的淸洗水混合），會生成毒性氣體。因此，須有移除 氨和氟化物的改良法。 本發明之目的和槪述 經濟部智慧財產局員工消費合作社印製 據此，本發明的目的是提出一種用以移除廢水中之氨 和氟化物的改良系統和方法。特別地，本發明者已經發現 到：以前技藝用以移除廢水中之氟化物的方法可以藉由在 添加鈣鹽以使氟化鈣沉澱之前以氧化劑處理廢水而以化學 力破壞氨的方式獲得顯著改善。本發明的另一目的是要降 低自廢水移除氟化物的成本，其藉由降低化學要求及形成 更易於拋棄的低體積廢液流而達成。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 574144 A7 __ B7 五、發明説明（4 ) (請先閲讀背面之注意事項再填寫本頁) 一般而曰’本發明是一種在處理氟化物之gij ’以化學 方式破壞氨的方法。之後，此廢水以接近化學計量的鈣鹽 處理而使氟化鈣沉澱。最後，自廢水移除懸浮的固體。最 終步驟可以是傳統沉積槽或一些過濾系統。較佳固體移除 法是單一通過低壓高流率過濾步驟，如：得自MicroBar的 EnChem系統。選擇包括過量氧化物和副產物之中和反應及 以活性碳移除副產物。過量氧化劑和副產物之中和反應可 於過濾之前以化學方式進行。通常，當無固體的水以還原 劑處理和/或與活性碳接觸時，在過濾步驟之後進行更方 便。活性碳可藉化學吸收和反應地移除次氯酸鹽和氯胺。 活性碳亦有助於移除可能於廢水中形成之任何氯化的有機 物質。 經濟部智慧財產局工消費合作社印製 更特定言之，本發明提出一種處理廢水以降低氟化物 和氨濃度的方法。初時，使用氧化-還原電位測定裝置測 定廢水的氧化-還原電位。之後，添加足量氧化劑以將廢 水的氧化-還原電位提高至高於氯胺溶液。之後在廢水中 添加可溶解的鈣鹽，鈣鹽的添加量高於化學計量。可溶性 鈣鹽降低廢水中的氟化物溶解度並促使固態氟化鈣沉澱。 之後，在廢水中添加氧化物和氧化反應副產物中和劑，破 壞廢水中的過量氧化劑和氧化反應副產物。或者，可以在 固體分離步驟之後進行此程序。最後，廢水通入固體分離 系統，以將廢水分離成經處理的流體（懸浮固體含量較低 者）和濃縮物（懸浮固體含量較高者）。 本發明的優點中，有效使用鈣鹽，消除氯胺副產物及 ^紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 574144 A7 B7 五、發明説明（5 ) 易於使用和過濾。此方法可批次、半批次或連續流模式實 施。 (請先閲讀背面之注意事項再填寫本頁) 附圖簡沭 讀完本發明的詳細描述和所附申請專利範圍及參考附 圖之後，會更暸解本發明的這些和其他優點，附圖中： 附圖1是流程圖，用以說明本發明之方法可使用的處 理步驟順序。 附圖2是本發明之方法可使用的一個處理系統例的方 系統 稀釋槽 經濟部智慧財產局員工消費合作社印製 塊麗 10 1 2 14 16 2 0 2 2 2 4 2 6 3 0 3 2 3 4 3 6 4 0 氨濃度較低的廢水流系統 第一個反應槽 〇R P感知器 第二個反應槽 氟化物感知器 固體分離系統 第三個反應槽 輸送管 過濾系統 微濾槽 沉積或淤渣存放槽 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X297公釐） -8 - 574144 Α7 Β7 五、發明説明（6 ) 4 2 微濾膜陣列 4 4 壓濾器 (請先閲讀背面之注意事項再填寫本頁) 發_明詳沭 本發明者已發現一種用以自含有氨的廢水移除化物 的新方法，其大幅降低氟化鈣沉澱步驟的化學品添加需求 並因此大幅降低成本和固體生成。提出下列詳細描述。本 發明提出一種成本效益高之启含氨的廢水移除氟化物的方 法。 一般而言，本發明提出一種處理含氨和氟化物之工業 廢水的方法。標準前處理之後，先藉化學氧化反應降低氨 濃度。之後，添加可溶鹽（以鈣鹽爲佳）以形成固態氟化 物沉澱物。先前的步驟中破壞氨，提高了此沉澱步驟的效 能並因此降低化學添加需求和成本。添加一或多種適當的 中和劑，破壞留下的氧化物和氧化反應副產物。最後，在 排放或再利用廢水之前，藉過濾或沉積法移除固體。 經濟部智慧財產局員工消費合作社印製 更特定言之，如附圖1的流程圖所示者，測試輸入的 廢水以定出胺濃度1 0 0。若因濃度過高而無法被安全地 處理時，廢水經稀釋1 0 2。氨濃度非常高的廢水必須經 稀釋以免在氨氧化反應期間內過度加熱或形成氨氣煙霧。 之後，測定廢水，及，有須要時，藉由添加強酸或鹼地調 整至所欲P Η値1 0 6。p Η約6至8爲佳，以儘可能減 少毒性副產物之形成，Ρ Η約7至8最佳。可以使用鹼性 化合物將廢水的Ρ Η向上調整。一些例子包括氯氧化紳、 本紙張尺度通用中國國家標準（CNS ) Α4規格（210X297公釐） 574144 A7 ___ _B7______ 五、發明説明（7 ) 氫氧化鈉、石灰、消石灰、碳酸鈉和碳酸鈣。之後’以 〇R p感知器控制偵測氧化一還原電位（〇R p ) 1 1 0 (請先閲讀背面之注意事項再填寫本頁) ，以次氯酸鈉、次氯酸鉀、次氯酸鈣、氯、二氧化氯、臭 氧和過氧化氫及其他適當氧化劑破壞氨1 1 2 °也可以使 用測定廢水之氧化-還原電位的其他方法。只要所有的氨 被破壞，0 R P訊號改變成稀釋氧化劑溶劑的訊號而非氨 溶液的訊號1 1 4。 可藉滴定、離子特定電.極或其他適當裝置測定氟含量 。鈣離子以，如：可溶性鈣鹽，形式添加1 2 0。典型鹽 包括氯化鈣、溴化鈣、石灰、消石灰和硝酸鈣。亦可使用 溶解度較低的其他鈣鹽（如：硫酸鈣或碳酸鈣），特別是 作爲固態氟化物沉澱反應的一部分以代替直接溶液氟化物 沉澱方式。廢水的氨濃度以降至低於所須流出氟化物濃度 的2 0 %爲佳，鈣離子與氨和銨離子之錯合情況大幅減少 。鈣離子的添加率以約0 . 5 5至0 . 6 5莫耳鈣/莫耳 流入的氟爲佳。 經濟部智慧財產局員工消費合作社印製 此處，使用亞硫酸氫鈉、亞硫酸鈉、硫代硫酸鈉或其 他適當化學品，實質上破壞過量氧化劑及任何氯胺或其他 氧化反應副產物1 2 2。或者，可以使用過氧化氫破壞次 氯酸鹽或氯，之後可以使用亞硫酸氫鹽之類破壞氯胺。另 一實施例中，廢水通入活化或催化性碳床以吸收和吸附和 /或催化性破壞過量氧化劑和氯胺及其他氧化反應副產物 〇 氧化反應副產物和過量氧化劑之中和反應之後，藉固 ^紙張尺度適用中國國家標準（CNS ) A4規格（210X297公羡) -10- 574144 A7 B7 五、發明説明（8 ) (請先閲讀背面之注意事項再填寫本頁) 體分離系統自廢水移除沉潑的氟化與1 2 4。較佳情況中 ，混合物以無機和有機凝結劑和絮凝劑之混合物處理，以 提供大、不發黏的易過濾顆粒。此凝結劑和/或絮凝劑以 EnChem 0696 凝結劑、EnChem 9 0 2 5聚合型絮凝劑爲佳，或者是任何其他適當的廢水 處理凝結劑和絮凝劑（如：聚氯化鋁、氯化鋁、氯化鐵、 聚丙烯酸、聚胺）和可用於廢水絮凝物形成及沉積之其他 適當的有機絮凝劑中之一或多者。所得懸浮顆粒經任何慣 用過濾設備過濾，或者可以使用沉積槽。本發明的最佳形 式是使用EnChem 0696和EnChem 9〇2 5凝結劑和絮凝劑及Micro Bar EnChem單一流低壓袋 濾器組合品之組合，之後將固體抽至壓濾器（如美國專利 案第5 ·，9 0 4 ，8 5 3和5 ，9 0 0 ，2 2〇號中所述 者’炫將其中所述者全數列入參考）。 經濟部智慧財產局員工消費合作社印製 本發明的另一對等的較佳實施例中，將過量氧化劑和 氧化反應副產物予以中和的步驟1 2 2可於使廢水通過固 體分離系統的步驟1 2 4之後進行。此實施例的較佳情況 中，中和步驟1 2 2使用活性碳床完成。已經知道：如果 使用活性碳處理有大量懸浮固體的水，活性碳（有時稱爲 催化性碳）床會迅速污染。 用以實施本發明的適當廢水處理系統示於附圖2。附 圖2所示者是用以含氨和氟化物之廢水的處理系統1 0。 廢水先輸送至稀釋槽1 2。如果已經知道廢水的氨濃 度高，其以另一氨濃度較低的廢水流系統1 4稀釋。在稀 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -11 - 574144 Α7 Β7 五、發明説明（9 ) (請先閲讀背面之注意事項再填寫本頁) 釋槽1 2中，反應槽1 2中的廢水p Η以適當鹼性化合物 (如：氫氧化鉀、氫氧化鈉、石灰或消石灰）調整至約7 至8範圍內。之後，廢水流入第一個反應槽1 6，其以備 有感知器2 0用以測定廢水的氧化-還原電位爲佳。使用 〇R Ρ感知器2 0的迴饋，添加氧化劑直到廢水的〇R Ρ 相當於稀釋次氯酸鹽溶液的〇R Ρ爲止。較佳氧化劑選自 次氯酸鈉、15或鉀、氯、臭氧、二氧化氯和過氧化氣。第 一個反應槽1 6中的廢水攪拌一段時間以混合化學品，以 發生反應。攪拌時間長短視第一個反應槽和污染物的初濃 度而定，通常是至少約1 0分鐘。用於連續流系統，在第 一個反應槽的較佳平均停留時間在約1 0分鐘至3小時範 圍內，1 0至3 0分鐘最佳。就批次和半批次系統而言， 最低處理時間以1 0分鐘爲佳，最少3 0分鐘最佳。 經濟部智慧財產局員工消費合作社印製 一旦完成氨的氧化反應，廢水進入第二個反應槽2 2 。測定氟化物濃度，以使用氟化物感知器2 4測定爲佳。 可溶性鈣鹽（以選自石灰、消石灰、氯或溴化鈣和硝酸齡 爲佳）加至廢水中以沉殿出氟化齡。可溶性15鹽的添加率 以約0 · 5 5至0 . 6 5莫耳鈣/莫耳廢水中的氟化物爲 佳。以在添加可溶性鈣鹽之後，在第二個反應槽2 2的廢 水中添加一或多種氧化劑和氧化反應副產物中和劑爲佳。 這些中和劑可以包括第二種氧化劑（如：過氧化氫）及還 原劑（如：亞硫酸氫鈉、亞硫酸鈉和硫代硫酸鈉。或者可 以僅使用還原劑。過氧化氫是第二種氧化劑，其迅速破壞 次氯酸鹽和一些氯胺。此還原劑也會破壤次氯酸鹽和任何 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） -12- 574144 A7 B7 五、發明説明（10) 氯胺。 (請先閲讀背面之注意事項再填寫本頁) 第二個〇R P感知器（未示於附圖2 )可摻入第二個 反應槽2 2中，以估計中和劑的適當量。所欲結果是破壞 過量氧化劑和任何氯胺或在第一個反應槽1 6中形成的氧 化反應副產物。第二個反應槽2 2的尺寸應使得廢水溶液 的停留時間約至少3分鐘，但建議使用較長時間。因爲實 際廢水濃度改變，所以停留時間以1 0至3 0分鐘爲佳。 氟化鈣沉澱及氧化反應副產物和過量的氧化劑在第二 個槽2 2中和之後，廢水流入固體分離系統2 6。此固體 分離系統以包括第三個反應槽3 0以添加一或多種有機和 無機凝結和絮凝劑爲佳。這些有機和無機凝結和絮凝劑以 選自 E n C h e m 0 6 9 6 凝結劑、E n C h e m 9 0 2 ‘5聚合物或可用於廢水絮凝物形成和沉積的其他有 機絮凝劑（如：聚氯化鋁、氯化鋁、氯化鐵、聚丙烯酸和 聚胺）。 經濟部智慧財產局員工消費合作社印製 或者，沉澱和/或絮凝劑可經由第二2 2和第三個反 應槽3 0之間的輸送管3 2中的管路內混合器（未示）添 加。一個實施例中，3 0 %以鋁爲基礎的凝結劑溶液以約 1毫升/加侖廢水濃度添加，陽離子絮凝劑以約1 〇 〇 P P m活性物質濃度添加。較佳情況中，添加沉澱和/或 絮凝劑時，將第三個反應槽3 0中的廢水ρ Η向上調整至 Ρ Η至少7，以調整至ρ Η約7至9爲佳。在此Ρ Η範圍 內，在廢水中形成帶有污染物的不溶解顆粒或化合物。另 一實施例中，聚合物或其他凝結劑可以視情況地加至第三 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -13- 574144 A7 B7 五、發明説明（11) 個反應槽3 0中以有助於形成不溶解的北合物。 一旦形成，帶有污染物的顆粒藉幫浦或重力進入過爐 系統3 4。可以使用任何適當的過濾系統。附圖2所示者 僅爲適當過濾系統的一個例子。附圖2中所示的此過濾系 統3 4通常包含膜濾系統，如：美國專利案第 5 ’ 8 7 1 ，6 4 8和5 ，9 0 4，8 5 3號中所述的微 濾系統，茲將其中所述者全數列入參考。此實例中，過濾 系統通常包括一或多個濾器或微濾槽3 6和沉積或淤渣存 放槽4 0。可以使用逆沖槽（未示），其以位於濾槽3 6 之前爲佳。濾槽3 6以兩種模式操作；即，過濾槽操作模 式和濾槽逆沖模式。濾槽3 6通常包括成管狀、、套〃構形 的濾膜4 2。此膜套置於狹長管上以免濾套於使用期間內 瓦解。此膜材料是各種來源的市售品，以孔隙尺寸在 〇 _ 5至1微米範圍內者爲佳，孔隙尺寸1微米最佳。 此操作模式期間內，帶有污染物的顆粒經脫水並自廢 水中濾出。此廢水自瀘槽抽經膜，廢水通過膜，顆粒未通 過而是累積在膜表面的外側。乾淨的類水溢流離開濾槽頂 部以丟棄或再利用。此乾淨的廢水幾乎沒有污染物固體或 顆粒，且總懸浮固體濃度通常低於1 〇 p p m。 更特定言之，濾槽以配備微濾膜陣列4 2 (如： E n C h e m 系統）爲佳。較佳情況中，此微濾膜由管 狀v套〃構形構成以儘可能提高表面積。此膜套置於狹長 的載體管上以免膜套會於使用期間內瓦解。爲了要達到高 流率和通量，可以使用多個膜或膜組（各者含有多個濾套 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 項再填办 經濟部智慧財產局員工消費合作社印製 -14- 574144 A7 B7 五、發明説明（12) )。此微濾膜的孔隙尺寸以在0 · 5微米至1 0微米範圍 內爲佳，〇 . 5至1 _ 0微米更佳。已經發現到處理的廢 (請先閲讀背面之注意事項再填寫本頁) 水通過0 . 5至1微米微濾膜的流率可以在1 0 0 G F D 至1 5 0 0 G F D (加侖/平方英呎濾膜面積/天）範圔 內。 逆沖模式中，廢水流中止，淸潔的水反向流通過濾膜 4 2以移動固體。移動的固體自微濾槽3 6底部排出到達 固體存放槽4 0。剩餘逆沖流循環至第三個反應槽3 0以 在固體分離系統2 6中進一步處理。固體存放槽4 0中收 集的固體週期性地引至壓濾器4 4以脫水。來自壓濾器的 濾液循環回到第三個反應槽3 0以移除固體。 除了前述的E n C h e m 註冊商品（其用於 E n C h e m 濾器）以外，其他過濾法和被動沉積法、 經濟部智慧財產局員工消費合作社印製 任何標準廢水凝結和絮凝無機和有機物可用於固體分離步 驟。但是，並非所有的組合效果皆與E n C h e m 濾器 相同。這些包括鐵明礬、氯化鋁、硫酸鉀鋁或氯化鉀、聚 氯化鋁、氯化鐵、硫酸鐵、聚合型有機絮凝劑和此技藝中 已知之其他的廢水處理凝聚和絮凝化學品。僅 E n C h e m 所有化學品可用於E n C h e m 過濾法 〇 本發明的另一實施例中，廢水中的氧化反應副產物和 過量氧化劑可以藉由使廢水通過活性碳床而中和。此實施 例中，中和步驟於前述過瀘步驟之後進行。如果處理的水 中之懸浮固體含量高，碳床易迅速被污染，因此必須在以 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公酱) _15_ 574144 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（13) 活性碳處理之前先移除固體。催化性活性碳常用以破壞過 量過氧化氫、氯、次氯酸鹽和氯胺。過量氧化劑與高表面 積碳反應，後者氧化成二氧化碳。此活性碳亦可吸收氯化 的有機化合物，如：四氯化碳和氯仿，其可能在與次氯酸 鹽或其他含氯的氧化劑反應時，由微量有機化合物形成。 實驗 下面的實例僅作說明之用，不欲對本發明造成任何限 制。本發明以稀氟化物沖洗液和緩衝的氧化物鈾刻（ B〇E )溶液之組合廢水流進行，其量約2 0 0 0立方米 /月。 特別地，B ◦ E溶液本身的量約7 5立方米/月，可 能增加至約1 5 0立方米/月。即使體積小，氟化物和氨 的總量仍高。此B〇E廢液流佔來自設備的氟化物廢料之 約 5 0 % 〇 一個實例中，氟化銨濃度在3 - 8重量％範圍內。有 〇.2 - 0 . 6重量％磷酸三銨。矽石濃度低，僅幾百 p p m。無大量有機物存在。收集2 0立方米樣品，發現 含5 . 2重量％氟化物。測定進入時的P Η，結果約6， 約須3 0 %鹼將ρ Η提高至7 - 8。試驗顯示添加約5 -7體積0%鹼可達最佳ρΗ7 — 8範圍。 由前述標準，實施本發明之步驟包括：以次氯酸鹽破 壞氨，以過氧化氫破壞殘留氧化劑和副產物，添加氯化鈣 ，之後添加凝結劑和/或絮凝劑（如：E n C h e m 本紙張尺度適用中國國家標準（CNS ) A4規格（21 OX 297公釐） (請先閲讀背面之注意事 —0 .項再填. 裝-- :寫本頁) 、11 Φ •16- 574144 Α7 Β7 五、發明説明（14) 0 6 9 6和E n C h e m 9 ◦ 2 5 )及之後過爐。整個 (請先閱讀背面之注意事項再填寫本頁) 程序可以連續批次法順利地進行，不具複雜性且連續法的 不確定性少。 此特定實例中的化學品濃度過高而無法直接處理。較 佳情況中，此溶液稀釋至約2 5 %強度。一個實施例中， 系統包含一個累積槽和一個批料處理槽，其與過濾系統（ 以2 0克E n C h e m 過瀘系統爲佳）直接連接。此構 造使得一個混合器、一組感知器和一組供添加化學品之用 的幫浦皆位於一個槽中。特定言之，實施下列步驟： 1 .在約1 5 0 0加侖的累積槽中累積一日的B〇E 廢水，基本上量約7 5 0 — 1 0 0 0加侖。 2 .將此抽至5 0 0 0加侖反應槽中。廢水來自消石 灰反應器的乾淨壓濾器流出水稀釋至約2 5 %濃度。注意 此爲分離氟化物沉滠處理步驟，其用以處理氨含量低之帶 有氟化物的廢料。以壓濾器移除此固體，於p Η高於9時 經濟部智慧財產局員工消費合作社印製 ，所得透明液體含有一些可溶解的鈣。此僅使用存在之可 相配伍的廢水達成。任何適當的自來水或流程水可用於稀 釋。 3 .此反應槽必須抽真空以移除會於處理期間內釋出 的氨，.且可藉由引至可資利用之已有之用於氨的設備滌氣 系統中而達成。使用3 0 %鹼中和此Β〇Ε至約ρ Η 7 · 5。 4 .檢視〇R ρ感知器。添加次氯酸鈉溶液直到〇R Ρ讀値改變且維持穩定爲止。視情況地，亦可以使用氨感 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） -17- 574144 A7 B7 五、發明説明（15) 知器。此實例的目標是殘留的氨低於5 〇 p p m。 (請先閱讀背面之注意事項再填寫本頁) 5 ·添加3 0 %過氧化氫以中和殘留的次氯酸鹽和氯 胺。如果夠小心地進行氨之中和反應，僅有些微過量的次 氯酸鹽和氯胺，所須的過氧化氫量也少。較佳情況中，以 〇R P計偵測添加量。 6 .使離子敏感電極（I S E )讀取氧化物量。 I S E應爲自身潔淨模式或有濾器防止結塊和阻塞。 7 .以0 · 5 5 C a / .1 . 〇 F比例添加氯化鈣溶液 。使其於PH7 - 8攪拌及反應3 0分鐘。 8 _再度讀取氟化物I S E。視需要地重覆步驟7。 其目標是要達到低於5 0 P P m氟化物。使用緩慢的批料 處理系統且氨離開，已經發現到此由僅略大於化學計量添 加的鈣達成。 9 .添加 EnChem 0696 和 EnChem 9〇2 5使p Η維持7 — 8。 經濟部智慧財產局員工消費合作社印製 1 0 .調整至2 0 g P m過濾單元並使其運轉直到反 應槽掏空。乾淨的流出液進入下水道。淤渣直接進入適當 的壓濾器。如果批次槽的總體積約5 0 0 0加侖，則過濾 單元每天僅運作約4小時。此使得有許多時間進行批次處 理，得以在不改變設備的情況下，處理雙倍或三倍量。 前面關於本發明特定實施例和實例的描述用以說明和 敘述，雖然已經已經以前面的某些例子作說明，本發明不 在此限。不欲將本發明限於此處所揭示的特定形式，顯然 地，.由前述經驗能夠作出許多修飾、實施例和變化。希望 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -18- 574144 A7 B7 五、發明説明（16) 圍 箪 利 專 請 串 附 所 及 圍 》車 般 1 述 所 處 匕 ί 。 括況 含[f 圍等 範對 之的 Γπ^ 0—? 發它 本及 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -19-574144 Α7 Β7 V. Description of the invention (1) Relevant applications Nos. 2 3 5 and 9 9 2 are listed here (please read the notes on the back before filling this page) Related Provisional Patent Application No. 6 0 Application for reference on September 26, 2000. Invention Field This invention relates generally to wastewater treatment. More specifically, the present invention proposes an improved system and a more efficient method for treating industrial wastewater to continuously remove ammonia and fluoride by chemical destruction of ammonia, treatment and filtration with nearly stoichiometric calcium salts, and filtration. Background of the invention Intellectual property of the Ministry of Economic Affairs β) Member X Consumer cooperatives in the printing industry The processing of sandstone crystals with ammonium fluoride or difluorination before the tap water system may have lower emission limits than ammonia 'ammonia emission limits limit calcium precipitation, making processing Put the limit, develop a method of ammonia concentration, and also want to achieve extremely low. This consumes a large amount without solids. This buffered oxide etching method is used for semiconductor wafers. This buffered oxide etch requires the use of highly concentrated ammonium, which ultimately remains in the semiconductor wastewater. At discharge, fluoride must be removed from the wastewater stream and the area is 5 p p m. It may also be necessary to first remove as little as 5 p p m from the wastewater. In addition, ammonia interferes with fluorination processes and must use large excess calcium salts. To comply with ammonia and / or fluoride seeding treatment methods in wastewater. Air scrubbing is a way to reduce wastewater. Air scrubbing must be carried out at an increased ammonia concentration of alkaline p 能量, the energy in a hot solution with ρ Η greater than 10, a large amount of alkali must be added, and the Chinese paper standard (CNS) A4 specification must be applied to the paper size in the wastewater. (210 × 297 mm) -4- 574144 B7 V. Description of the invention (2) (Please read the precautions on the back before filling this page), except for chemically destroying ammonia except for this method, which will transform it into a gas phase. It is washed into the acidic absorption solution or discharged into the environment. Fluoride is not easily removed by air, so it must be removed in a separate step before or after air scrubbing. Reverse osmosis (RO) is another wastewater treatment technique that can be used to treat fluoride and ammonia. However, Ro is sensitive to membrane contamination because it forms scales or has biological growth on the filter membrane. Removal of calcium, magnesium and other scale-forming substances prior to the step, or more often by acidifying the wastewater to prevent precipitation of calcium carbonate and magnesium, or by adding dispersants to block Dirty to avoid the formation of scales. Solvents (such as alcohols or ketones) and other chemical or biological oxygen requirements must also be removed to prevent organisms from growing on the membrane. Acidified R ◦ The concentrate contains ammonia and fluoride preferentially, but ammonia is not chemically destroyed when scrubbed with air. Fluoride is usually removed after the Ro concentration step. However, an increase in the ammonia concentration in the concentrate will prevent the precipitation of calcium fluoride, in which case a large excess of calcium salt must be used. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Another processing technology is ion exchange using cation exchange resins. However, because the resin must be regenerated, this usually results in high chemical costs, so this method has little effect on wastewater with high ammonia concentration. As for the method previously discussed, ammonia is almost completely moved from the wastewater to a different medium (here, a concentrated acid waste stream). To avoid ammonia scrubbing, the p Η and concentration of the incoming wastewater must be closely monitored and adjusted. Other cations (such as 15, magnesium, sodium, etc.) can interfere with ammonia removal. Because of the formation of buffered ammonium fluoride compounds, fluoride can interfere with the effective removal of ammonia; ammonia can interfere with fluoride precipitation. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) " " _5_ 574144 B7 V. Description of the invention (3) (Please read the notes on the back before filling this page) Biological treatment has been used Destroy ammonia in wastewater. However, such a treatment is slow and rather ineffective. A treatment tank with considerable cost and space requirements must be constructed. It is sensitive to temperature and ionic strength and other compounds present in the wastewater, and requires the assistance of organic matter and fertilizers. Because only low levels of fluoride are compatible with biological treatment, this wastewater must be diluted. Due to the limitation caused by the solubility of calcium fluoride (approximately 16 p P m), it is necessary to dilute and suppress the precipitation of fluoride before treating the wastewater. Therefore, regardless of the initial concentration of fluoride, a similar concentration of fluorinated effluent is reached due to precipitation, which makes the total amount of fluoride discharged by the treatment process increase with dilution. This is why the effect of treating high concentration fluoride is better than that of treating low concentration fluoride. Ammonia has also been removed by chemical destruction of hypochlorite, but with limited effectiveness. The presence of organic substances can form halogenated organic compounds. Residual hypochlorite is toxic when mixed with unreacted ammonia (for example, treated wastewater mixed with other untreated washing water). Therefore, there must be improved methods for removing ammonia and fluoride. Purpose and description of the present invention Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Accordingly, the object of the present invention is to propose an improved system and method for removing ammonia and fluoride in wastewater. In particular, the present inventors have discovered that the prior art method for removing fluoride from wastewater can be obtained by chemically destroying ammonia by treating the wastewater with an oxidant before adding calcium salts to precipitate calcium fluoride Significant improvement. Another object of the present invention is to reduce the cost of removing fluoride from wastewater, which is achieved by reducing chemical requirements and forming a lower volume waste stream that is easier to discard. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 574144 A7 __ B7 V. Description of the invention (4) (Please read the precautions on the back before filling this page) Generally speaking, the present invention is a A method for treating gij 'of fluoride by chemically destroying ammonia. This wastewater is then treated with near-stoichiometric calcium salts to precipitate calcium fluoride. Finally, suspended solids are removed from the wastewater. The final step can be a traditional sedimentation tank or some filtration system. The preferred solids removal method is a single low pressure, high flow rate filtration step, such as the EnChem system from MicroBar. Options include neutralization of excess oxides and by-products and removal of by-products with activated carbon. Neutralization of excess oxidant and by-products can be carried out chemically before filtration. Generally, when solid-free water is treated with a reducing agent and / or is contacted with activated carbon, it is more convenient to perform it after the filtration step. Activated carbon removes hypochlorite and chloramine by chemical absorption and reaction. Activated carbon also helps to remove any chlorinated organic matter that may form in wastewater. Printed by the Industrial and Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy More specifically, the present invention proposes a method for treating wastewater to reduce the concentration of fluoride and ammonia. In the beginning, the oxidation-reduction potential of the wastewater was measured using an oxidation-reduction potential measuring device. After that, a sufficient amount of oxidant was added to raise the oxidation-reduction potential of the waste water to be higher than that of the chloramine solution. Later, soluble calcium salts are added to the wastewater, and the amount of calcium salts added is higher than the stoichiometric amount. Soluble calcium salts reduce the solubility of fluoride in wastewater and promote precipitation of solid calcium fluoride. After that, oxides and oxidation reaction by-product neutralizers are added to the wastewater to destroy excess oxidants and oxidation reaction by-products in the wastewater. Alternatively, this procedure can be performed after the solid separation step. Finally, the wastewater is passed to a solids separation system to separate the wastewater into treated fluids (lower suspended solids) and concentrates (higher suspended solids). Among the advantages of the present invention, the effective use of calcium salts, elimination of chloramine by-products, and paper size are applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) 574144 A7 B7 V. Description of the invention (5) Easy to use and filter. This method can be implemented in batch, semi-batch, or continuous flow mode. (Please read the notes on the back before filling this page) Brief description of the drawings After reading the detailed description of the present invention and the scope of the attached patent application and referring to the drawings, you will know more about these and other advantages of the present invention. Fig. 1 is a flowchart illustrating the sequence of processing steps that can be used with the method of the present invention. Figure 2 is an example of a processing system that can be used in the method of the present invention. The square system dilution tank is printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and the Consumer Consumption Cooperative. 10 1 2 14 16 2 0 2 2 2 4 2 6 3 0 3 2 3 4 3 6 4 0 Wastewater flow system with low ammonia concentration. First reaction tank. RP sensor. Second reaction tank. Fluoride sensor. Solid separation system. Third reaction tank. Pipeline filtration system. Microfiltration tank deposition or sludge. Storage tank The paper size is in accordance with Chinese National Standard (CNS) A4 (210 X297 mm) -8-574144 Α7 Β7 V. Description of the invention (6) 4 2 Microfiltration membrane array 4 4 Pressure filter (Please read the note on the back first) (Please fill in this page again). Develop_Explain in detail. The present inventors have discovered a new method for removing compounds from ammonia-containing wastewater, which greatly reduces the need for adding chemicals in the calcium fluoride precipitation step and therefore significantly reduces costs and Formation of a solid. The following detailed description is proposed. The present invention proposes a cost-effective method for removing fluoride from ammonia-containing wastewater. Generally speaking, the present invention proposes a method for treating industrial wastewater containing ammonia and fluoride. After standard pre-treatment, first reduce the ammonia concentration by chemical oxidation. Thereafter, a soluble salt (preferably a calcium salt) is added to form a solid fluoride precipitate. The destruction of ammonia in the previous step increases the effectiveness of this precipitation step and therefore reduces chemical addition requirements and costs. Add one or more appropriate neutralizing agents to destroy the remaining oxides and oxidation reaction by-products. Finally, the solids are removed by filtration or sedimentation before the wastewater is discharged or reused. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs More specifically, as shown in the flow chart in Figure 1, the input wastewater is tested to determine the amine concentration of 100. If it cannot be treated safely due to the high concentration, the wastewater is diluted by 102. Wastewater with very high ammonia concentrations must be diluted to avoid excessive heating or formation of ammonia fumes during the ammonia oxidation reaction. After that, the waste water is measured and, if necessary, adjusted to the desired PΗ 値 106 by adding a strong acid or alkali. P 佳 is preferably about 6 to 8 in order to minimize the formation of toxic by-products. P Η is about 7 to 8 is the best. The pH of the wastewater can be adjusted upwards using basic compounds. Some examples include Chlorine Oxidation, the Chinese Standard (CNS) A4 size of this paper (210X297 mm) 574144 A7 ___ _B7______ 5. Description of the invention (7) Sodium hydroxide, lime, slaked lime, sodium carbonate and calcium carbonate. Afterwards, the oxidation-reduction potential (〇R p) is detected by the 〇 R p sensor control (〇 R p) 1 1 0 (please read the precautions on the back before filling this page), with sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, chlorine, Chlorine dioxide, ozone and hydrogen peroxide and other suitable oxidants destroy ammonia 1 1 2 ° Other methods of measuring the oxidation-reduction potential of wastewater can also be used. As long as all ammonia is destroyed, the 0 R P signal changes to a signal that dilutes the oxidant solvent instead of a signal that is ammonia solution 1 1 4. The fluorine content can be determined by titration, ion-specific electrodes or other suitable devices. Calcium ions are added in the form of, for example, soluble calcium salts. Typical salts include calcium chloride, calcium bromide, lime, slaked lime, and calcium nitrate. Other calcium salts with lower solubility (such as calcium sulfate or calcium carbonate) can also be used, especially as part of the solid fluoride precipitation reaction instead of direct solution fluoride precipitation. The ammonia concentration of the wastewater is preferably reduced to less than 20% of the required fluoride concentration, and the mismatch of calcium ions with ammonia and ammonium ions is greatly reduced. The addition rate of calcium ions is preferably about 0.55 to 0.65 mol calcium / mole inflowing fluorine. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Here, the use of sodium bisulfite, sodium sulfite, sodium thiosulfate, or other appropriate chemicals substantially destroys excess oxidants and any chloramines or other oxidation by-products 1 2 2. Alternatively, hypochlorite or chlorine can be destroyed using hydrogen peroxide, and then chloramine can be destroyed using bisulfite or the like. In another embodiment, the wastewater is passed into an activated or catalytic carbon bed to absorb and adsorb and / or catalytically destroy excess oxidants and chloramines and other oxidation reaction by-products. After the oxidation reaction by-products and excess oxidants are neutralized, Borrowing ^ Paper size applies to Chinese National Standard (CNS) A4 specification (210X297 public envy) -10- 574144 A7 B7 V. Description of the invention (8) (Please read the precautions on the back before filling this page) Remove the drowsy fluoride with 1 2 4. Preferably, the mixture is treated with a mixture of inorganic and organic coagulants and flocculants to provide large, non-tacky, easily filterable particles. The coagulant and / or flocculant is preferably EnChem 0696 coagulant, EnChem 9 0 2 5 polymeric flocculant, or any other appropriate wastewater treatment coagulant and flocculant (eg, polyaluminum chloride, aluminum chloride , Ferric chloride, polyacrylic acid, polyamine) and other suitable organic flocculants that can be used for the formation and deposition of wastewater floes. The resulting suspended particles are filtered through any conventional filtering equipment, or a sedimentation tank may be used. The best form of the present invention is a combination of EnChem 0696 and EnChem 905 coagulant and flocculant and Micro Bar EnChem single-flow low-pressure bag filter combination, and then the solid is pumped to the filter (such as US Patent No. 5 · , 9 0 4, 8 5 3 and 5, 9 0 0, 2 2 0 'Xuan will include all of them in the reference). In another preferred embodiment of the present invention, which is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the step of neutralizing excess oxidant and oxidation reaction by-products 1 2 2 can be used to pass wastewater through a solid separation system Perform after 1 2 4. In the preferred case of this embodiment, the neutralization step 1 2 2 is performed using an activated carbon bed. It is known that if activated carbon is used to treat water with a large amount of suspended solids, the activated carbon (sometimes referred to as catalytic carbon) bed will quickly contaminate. A suitable wastewater treatment system for implementing the present invention is shown in Figure 2 of the accompanying drawings. The one shown in Figure 2 is a treatment system 10 for wastewater containing ammonia and fluoride. The wastewater is first transferred to the dilution tank 12. If it is known that the wastewater has a high ammonia concentration, it is diluted with another wastewater stream system with a lower ammonia concentration. Applicable Chinese National Standard (CNS) A4 specification (210X297 mm) for thin paper scales -11-574144 Α7 Β7 V. Description of the invention (9) (Please read the notes on the back before filling this page) Release slot 1 2 The wastewater pΗ in the reaction tank 12 is adjusted to a range of about 7 to 8 with an appropriate basic compound (such as potassium hydroxide, sodium hydroxide, lime or slaked lime). After that, the wastewater flows into the first reaction tank 16 which is preferably provided with a sensor 20 for measuring the oxidation-reduction potential of the wastewater. Using the feedback from the ORP sensor 20, the oxidant was added until the ORP of the wastewater was equivalent to the ORP of the diluted hypochlorite solution. Preferred oxidants are selected from sodium, 15 or potassium hypochlorite, chlorine, ozone, chlorine dioxide and peroxide. The wastewater in the first reaction tank 16 is stirred for a period of time to mix the chemicals for the reaction to take place. The length of the stirring time depends on the initial concentration of the first reaction tank and the contaminants, and is usually at least about 10 minutes. For continuous flow systems, the preferred average residence time in the first reaction tank is in the range of about 10 minutes to 3 hours, with 10 to 30 minutes being optimal. For batch and semi-batch systems, the minimum processing time is preferably 10 minutes, and the minimum is 30 minutes. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Once the ammonia oxidation reaction is completed, the wastewater enters the second reaction tank 2 2. The fluoride concentration is preferably measured using a fluoride sensor 24. Soluble calcium salts (preferably selected from the group consisting of lime, slaked lime, chlorine or calcium bromide and nitric acid age) are added to the wastewater to give the fluoride age. The addition rate of the soluble 15 salt is preferably about 0.55 to 0.65 mol calcium / fluoride in mol wastewater. It is preferable to add one or more oxidizing agents and oxidation reaction by-product neutralizing agents to the waste water of the second reaction tank 22 after adding the soluble calcium salt. These neutralizers can include a second oxidant (such as: hydrogen peroxide) and a reducing agent (such as: sodium bisulfite, sodium sulfite, and sodium thiosulfate.) Or you can use only reducing agents. Hydrogen peroxide is the second oxidant It quickly destroys hypochlorite and some chloramines. This reducing agent will also break hypochlorite and any paper size applicable to China National Standard (CNS) A4 specifications (210X 297 mm) -12- 574144 A7 B7 V. Description of the invention (10) Chloramine (Please read the notes on the back before filling this page) The second ORP sensor (not shown in Figure 2) can be incorporated into the second reaction tank 22, To estimate the appropriate amount of neutralizing agent. The desired result is the destruction of excess oxidants and any chloramines or by-products of oxidation reactions formed in the first reaction tank 16. The second reaction tank 22 should be sized so that the wastewater solution The residence time is at least 3 minutes, but it is recommended to use a longer time. Because the actual wastewater concentration changes, the residence time is preferably 10 to 30 minutes. Calcium fluoride precipitation and oxidation reaction by-products and excess oxidant in the second Slots 2 2 neutralized After that, the wastewater flows into the solid separation system 26. The solid separation system preferably includes a third reaction tank 30 to add one or more organic and inorganic coagulants and flocculants. These organic and inorganic coagulants and flocculants are selected from E n C hem 0 6 9 6 coagulant, E n C hem 9 0 2 '5 polymer or other organic flocculants (eg: polyaluminum chloride, aluminum chloride, ferric chloride) , Polyacrylic acid and polyamine). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Alternatively, the precipitation and / or flocculant can be passed through the tube in the transfer tube 32 between the second 22 and the third reaction tank 30. Add in-circuit mixer (not shown). In one embodiment, a 30% aluminum-based coagulant solution is added at a concentration of about 1 ml / gallon of wastewater, and a cationic flocculant is added at a concentration of about 1,000 ppm of active material. In a preferred case, when adding a precipitation and / or flocculant, the wastewater ρ 中 in the third reaction tank 30 is adjusted upward to at least P 以, and preferably adjusted to ρ Η about 7 to 9. Here Within the range of P ，, pollutants are formed in the wastewater. Dissolve particles or compounds. In another embodiment, polymers or other coagulants can be added to the third paper as appropriate. Applicable to China National Standard (CNS) A4 (210 × 297 mm) -13- 574144 A7 B7 V. DESCRIPTION OF THE INVENTION (11) Reactors 30 to assist in the formation of insoluble compounds. Once formed, particles with contaminants enter the furnace system by pump or gravity 34. Any appropriate filtration may be used The system shown in FIG. 2 is only an example of a suitable filtration system. The filtration system 3 4 shown in FIG. 2 usually includes a membrane filtration system, such as: US Patent Nos. 5 '8 7 1, 6 4 8 And the microfiltration system described in Nos. 5,104,8,53, all of which are hereby incorporated by reference. In this example, the filtration system typically includes one or more filters or microfiltration tanks 36 and sedimentation or sludge storage tanks 40. A backwash tank (not shown) can be used, which is preferably located before the filter tank 3 6. The filter tank 36 is operated in two modes; that is, the filter tank operation mode and the filter tank backflush mode. The filter tank 36 usually includes a filter membrane 4 2 in a tubular, sleeve-shaped configuration. This membrane sleeve is placed on an elongated tube to prevent the filter sleeve from disintegrating during use. This membrane material is a commercially available product from various sources, preferably having a pore size in the range of 0 to 5 micrometers, and having a pore size of 1 micrometer is the best. During this operating mode, particles with contaminants are dehydrated and filtered out of the waste water. This wastewater was pumped through the tank through the membrane, the wastewater passed through the membrane, and the particles did not pass but accumulated on the outside of the membrane surface. Clean water-like overflow leaves the top of the filter tank for disposal or reuse. This clean wastewater has almost no pollutant solids or particles, and the total suspended solids concentration is usually below 10 p p m. More specifically, the filter tank is preferably equipped with a microfiltration membrane array 4 2 (such as an E n C h e m system). Preferably, the microfiltration membrane is composed of a tubular v-jacket configuration to maximize surface area. The sleeve is placed on a long and narrow carrier tube to prevent the sleeve from disintegrating during use. In order to achieve high flow rate and throughput, multiple membranes or membrane groups can be used (each contains multiple filter sleeves. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)) (Please read the note on the back first) Please fill in this page again for the items), and then fill in the printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -14-574144 A7 B7 V. Description of Invention (12)). The pore size of the microfiltration membrane is preferably in a range of 0.5 μm to 10 μm, and more preferably 0.5 to 1 μm. Waste treatment has been found (please read the precautions on the back before filling this page). The flow rate of water through 0.5 to 1 micron microfiltration membrane can be between 1 0 0 GFD to 1 500 GFD (gallons per square inch) Ft filter area / day) within the range. In the recoil mode, the waste water flow is stopped, and clean water flows through the filter membrane 4 2 to move the solid. The moving solid is discharged from the bottom of the microfiltration tank 36 to the solid storage tank 40. The remaining countercurrent is recycled to the third reaction tank 30 for further processing in the solid separation system 26. The solids collected in the solid storage tank 40 are periodically led to the filter press 4 4 for dehydration. The filtrate from the filter was recycled back to the third reaction tank 30 to remove solids. In addition to the aforementioned En C hem registered products (which are used in En C hem filters), other filtration methods and passive sedimentation methods, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, any standard waste water condensed and flocculated inorganic and organic matter can be used Solid separation step. However, not all combinations are the same as En C h e m filters. These include iron alum, aluminum chloride, potassium aluminum sulfate or potassium chloride, polyaluminum chloride, iron chloride, iron sulfate, polymeric organic flocculants, and other wastewater treatment coagulation and flocculation chemicals known in the art. Only E n C h e m all chemicals can be used in the E n C h e m filtration method. In another embodiment of the present invention, oxidation reaction by-products and excess oxidants in the wastewater can be neutralized by passing the wastewater through an activated carbon bed. In this embodiment, the neutralization step is performed after the foregoing sterilization step. If the suspended solids content in the treated water is high, the carbon bed is easily contaminated, so the Chinese National Standard (CNS) A4 specification (210X297 male sauce) must be applied at this paper scale. A7 B7 V. Description of the invention (13) Remove solids before activated carbon treatment. Catalytic activated carbon is commonly used to destroy excess hydrogen peroxide, chlorine, hypochlorite and chloramine. Excess oxidants react with high surface carbon deposits, which oxidize to carbon dioxide. This activated carbon can also absorb chlorinated organic compounds, such as carbon tetrachloride and chloroform, which may be formed from trace amounts of organic compounds when reacted with hypochlorite or other chlorine-containing oxidants. Experiments The following examples are for illustration purposes only and are not intended to limit the invention in any way. The invention is carried out with a combined waste water stream of a dilute fluoride flushing solution and a buffered oxide of uranium oxide (BOE) solution in an amount of about 2000 cubic meters per month. In particular, the amount of the B◦E solution itself is about 75 cubic meters / month, and may increase to about 150 cubic meters / month. Even with small volumes, the total amount of fluoride and ammonia is still high. This BOE waste stream accounts for about 50% of the fluoride waste from the equipment. In one example, the ammonium fluoride concentration is in the range of 3-8% by weight. There is 0.2-0.6% by weight of triammonium phosphate. The silica concentration is low, only a few hundred p p m. No large amount of organic matter is present. A 20 cubic meter sample was collected and found to contain 5.2 wt% fluoride. The P 时 at the time of entry was measured, and the result was about 6, which required about 30% alkali to increase ρ 7 to 7-8. Tests have shown that the addition of about 5-7 vol. 0% alkali can achieve an optimal range of ρΗ7-8. According to the foregoing standards, the steps of implementing the present invention include: destroying ammonia with hypochlorite, destroying residual oxidants and by-products with hydrogen peroxide, adding calcium chloride, and then adding coagulants and / or flocculants (such as: E n C hem This paper size is in accordance with Chinese National Standard (CNS) A4 specification (21 OX 297 mm) (Please read the notes on the back-0. Then fill in. Installation-: write this page), 11 Φ • 16- 574144 Α7 Β7 V. Description of the invention (14) 0 6 9 6 and En C hem 9 ◦ 2 5) and subsequent furnace. The entire procedure (please read the precautions on the back before filling this page) The procedure can be performed smoothly in a continuous batch method without complexity and with less uncertainty in the continuous method. The concentration of chemicals in this particular example is too high to handle directly. Preferably, this solution is diluted to about 25% strength. In one embodiment, the system includes an accumulation tank and a batch processing tank, which are directly connected to the filtration system (preferably a 20 g E n C h e m filtration system). This construction places a mixer, a set of sensors, and a set of pumps for adding chemicals in a single tank. In particular, the following steps were performed: 1. A day of BOE wastewater was accumulated in an accumulation tank of approximately 1,500 gallons, and the amount was basically approximately 750-1000 gallons. 2. Draw this into a 5000 gallon reaction tank. The wastewater comes from the clean filter press of the ash removal ash reactor and the effluent water is diluted to a concentration of about 25%. Note This is a fluoridation separation treatment step, which is used to treat fluorinated waste with low ammonia content. This solid was removed with a filter press and printed at p Η above 9 when the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs employee printed the obtained transparent liquid containing some soluble calcium. This is achieved using only compatible wastewaters present. Any suitable tap or process water can be used for thinning. 3. The reaction tank must be evacuated to remove the ammonia that will be released during the treatment period, and can be achieved by introducing it into the available scrubbing system of existing equipment for ammonia. This BOE was neutralized to about ρ Η 7 · 5 with 30% base. 4. View the 0R ρ perceptron. The sodium hypochlorite solution was added until the OR reading changed and remained stable. Depending on the situation, ammonia can also be used. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -17- 574144 A7 B7 V. Description of the invention (15). The goal of this example is a residual ammonia below 50 p p m. (Please read the precautions on the back before filling out this page) 5 • Add 30% hydrogen peroxide to neutralize residual hypochlorite and chloramine. If ammonia neutralization is carried out with care, only a slight excess of hypochlorite and chloramine will require a small amount of hydrogen peroxide. In a preferred case, the amount of addition is detected on the basis of ORP. 6. Make the ion-sensitive electrode (I S E) read the amount of oxide. I S E should be in its own clean mode or have a filter to prevent clumping and blockage. 7. Add calcium chloride solution at a ratio of 0.5 · 5 C a / .1. 0 F. It was stirred and reacted at pH 7-8 for 30 minutes. 8 _ Read the fluoride I S E again. Repeat step 7 as necessary. The goal is to achieve less than 50 P P m fluoride. With a slow batch processing system and ammonia leaving, it has been found that this has been achieved by only slightly more than the stoichiometric addition of calcium. 9. Add EnChem 0696 and EnChem 905 to maintain p Η 7-8. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Adjust the filter unit to 20 g P m and run it until the reaction tank is empty. Clean effluent enters the sewer. The sludge goes directly to the appropriate filter. If the total volume of the batch tank is about 5000 gallons, the filter unit will only operate for about 4 hours per day. This allows a lot of time for batch processing, allowing for double or triple processing without changing equipment. The foregoing descriptions of specific embodiments and examples of the present invention have been used for illustration and description, although some of the foregoing examples have been described, the present invention is not limited thereto. Without intending to limit the invention to the specific forms disclosed herein, it will be apparent that many modifications, embodiments, and variations can be made from the foregoing experience. It is hoped that this paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -18- 574144 A7 B7 V. Description of the invention (16) For entrustment, please attach to the enclosed area and enclose the vehicle, as described in “Car 1” . Include the conditions that include [Γ ^ π ^ 0—? Of the equivalent range, and send it and (please read the precautions on the back before filling this page) Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs The paper standards are applicable to Chinese national standards (CNS) A4 specifications (210X297 mm) -19-