538006 A7 B7 五、發明説明（1> 相關申請案 相關之暫定專利申請案第60/235, 471號係 (請先閱讀背面之注意事項再填寫本頁} 於2 0 0 0年9月2 6日提出申請，茲將其中所述者列入 參考。 發明節圍 本發明一般係關於廢水處理。更特別地，本發明係關 於使用單一氟化物感應電極自廢水移除氟化物的系統和方 法。 發明背景 經濟部智慧財產局員工消費合作社印製 必須移除半導體製造和其他工業設備之廢水中的氟化 物。此爲昂貴的處理方式，其藉由添加鈣而達成。此鈣基 本上以石灰或氯化鈣溶液形式添加，其沉澱出不溶解的氟 化鈣。經化學處理以移除氟化劑的此廢水基本上經過濾或 者沉積於經特別設計的沉積槽。使用石灰或可溶性鈣鹽的 以前技藝方法的一個問題在於明顯過量添加鈣以確保氟化 物充份沉澱。使用石灰時，通常過量2 0 0 - 4 0 0 %化 學計量。但儘管如此，氟化物之移除仍不足。 未曾有系統地硏究高濃度氟化物（H F C )廢水處理 。高濃度氟化物定義爲超過2 0 0 0 p p m ( 2克/升） 氟化物，這樣高濃度存在會造成處理的額外問題。據此， 進一步硏究自動和經濟地移除廢水（特別是高濃度氟化物 廢水）中之氟化物的可行性。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 538006 A7 B7 五、發明説明（% 發明槪沭 (請先閲讀背面之注意事項再填寫本頁) 本發明的一個目的是要提出一種系統和方法，其依照 排放限制地連續自廢水移除氟化物，且同時最適當地使用 鈣鹽和提供良好過濾效果。本發明的另一目的是要提出系 統和方法，其可用於氟化物之分批處理，連續處理不規則 排放之具高濃度氟化物廢水，及連續處理具持續改變之高 濃度氟化物之廢水。 根據本發明，提出一種用以自廢水移除氟化物的系統 。此系統包含反應槽用以藉由添加鈣鹽而處理該廢水，濾 槽用以移除在反應槽中形成的沉澱氟化物，單一氟化物電 極，其位於反應槽的第一個輸入裝置以測定流入的廢水中 之氟化物濃度及提供輸出訊號，及程式可控制的控制器用 以控制該鈣鹽於該反應槽中之添加。此程式可控制的控制 器定義反應槽中之氟化物濃度的設定點並基於設定點及單 一氟化物電極提供的輸出訊號地自動控制鈣鹽之添加。 經濟部智慧財度局員工消費合作社印製 本發明的另一實施例中，此系統包含反應槽用以藉由 添加鈣鹽而處理該廢水，濾槽用以移除在反應槽中形成的 沉澱氟化物，第一個單一氟化物電極，其位於反應槽的第 一個輸入裝置以測定流入的廢水中之氟化物濃度及提供輸 出訊號，第二個單一氟化物電極，其位於濾槽的輸出裝置 以偵測經過濾的廢水中之氟化物濃度及提供輸出訊號，及 程式可控制的控制器用以控制該鈣鹽於該反應槽中之添加 。此程式可控制的控制器定義反應槽中之氟化物濃度設定 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -5- 538006 Μ Β7 五、發明説明（3 點並基於設定點及第一和第二個單一氟化物電極提供的輸 出訊號地自動控制鈣鹽之添加。 (請先閲讀背面之注意事項再填寫本頁) 此反應槽以備有ρ η感知器以測定進入反應槽之流入 廢水的ρ Η及提供輸出訊號。此Ρ Η感知器與控制器連接 ，此控制器定義反應槽中之Ρ Η設定點並基於ρ Η設定點 和Ρ Η感知器提供的輸出訊號地自動控制酸或鹼性溶液之 添力口。 一個實施例中，反應槽包含至少一個串聯的第一、第 二和第三個槽，各槽配備有Ρ Η感知器用以測定各槽的 Ρ Η。第一個槽中添加化學計量至1 2 5 %化學計量的鈣 鹽，該第二和第三個槽添加的鈣鹽量是加至第一個槽的5 至 2 5 %。 經濟部智慧財產局員工消費合作社印製 本發明的另一特點中，提出一種自廢水移除氟化物的 方法。此方法包含使用程式可控制的控制器定義氟化物濃 度設定點，使用第一個單一氟化物電極測定該廢水中的氟 化物濃度，自動在該廢水中添加鈣鹽，其添加量以控制器 定義的該設定點和藉第一個單一氟化物電極測得的氟化物 濃度爲基礎，並使用第二個單一氟化物電極測定流出廢水 中的氟化物濃度以確保符合排放限制。較佳情況中，加至 反應槽的鈣鹽量是化學計量至1 2 5 %化學計量。 此方法另可包含使用控制器定義ρ Η設定點及使用 Ρ Η感知器測定廢水的ρ Η ,及自動在廢水中添加酸或鹼 性溶液，其添加量以控制器定義的設定點和ρ Η感知器測 得的Ρ Η爲基礎。此ρ I-Ι設定點以定於6至9範圍內爲佳 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公) 7〇1 " 538006 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（4 。亦可在廢水中添加凝結劑和/或絮磁劑以有助於移除沉 澱的氟化物。 流入之欲藉本方法處理的廢水中所含氟化物濃度可持 續改變，由5 0至1 0，〇 〇 0 P P m。經本方法處理之 流出液中所含氟化物濃度低至2至1 0 p p m。 附圖簡沭 由本發明之詳細描述和所附申請專利範圍及附圖會更 瞭解本發明的其他目的和優點，附圖中： 附圖1是本發明使用單一氟化物電極移除廢水中之氟 化物的一個實施例之系統圖； 附圖2是於不同P Η時，可溶性氟化物與鈣的化學計 量之關係圖； 附圖3是在有Ν Η 4 +存在時，不同ρ η時，可溶性氟 化物與鈣的化學計量之關係圖； 附圖4是經根據本發明之實施例處理之氟化物排放物 和氟化物濃度圖； 附圖5是經根據本發明之另一實施例處理之氟化物排 料輸入和氟化物輸出濃度圖； 附圖6是根據本發明之實施例以約7立方米/小時小 量酸排料控制之ρ Η圖； 附圖7是根據本發明之實施例，系統ρ Η與非常大量 酸排料之關係圖； 附圖8是根據本發明之處理之前，未經處理之廢水之 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 7γΖ (請先閲讀背面之注意事項再填寫本頁) 538006 A7 B7 五、發明説明（3 高且相當穩定的氟化物濃度圖； 附圖9是根據本發明，附圖8中所示廢水的處理結果 圖； 附圖1 0是根據本發明之處理之前，未經處理之廢水 之變化相當大的氟化物濃度； 附圖1 1是根據本發明，附圖1 0中所示之廢水的處 理結果圖。 10 系統 15 程式可控制的控制器 2 0 反應槽 2 1 輸入裝置 2 2 單一氟化物電極 (請先閲讀背面之注意事項再填寫本頁)538006 A7 B7 V. Description of the Invention (1 > Provisional Patent Application No. 60/235, 471 related to related applications (Please read the precautions on the back before filling out this page}) September 20, 2000 An application is filed today, and the foregoing are incorporated herein by reference. The invention relates generally to wastewater treatment. More particularly, the invention relates to a system and method for removing fluoride from wastewater using a single fluoride sensing electrode. BACKGROUND OF THE INVENTION Employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs must print fluoride that must be removed from wastewater from semiconductor manufacturing and other industrial equipment. This is an expensive treatment method that is achieved by adding calcium. This calcium is basically made of lime or It is added in the form of a calcium chloride solution, which precipitates insoluble calcium fluoride. This wastewater, which is chemically treated to remove the fluorinating agent, is basically filtered or deposited in a specially designed sedimentation tank. Lime or soluble calcium salts are used. One problem with previous techniques is that a significant excess of calcium is added to ensure adequate precipitation of the fluoride. When lime is used, it is usually in excess of 200-400% stoichiometry. In spite of this, the removal of fluoride is still insufficient. The treatment of high-concentration fluoride (HFC) wastewater has not been systematically investigated. High-concentration fluoride is defined as more than 2000 ppm (2 g / l) fluoride, such a high concentration There are additional problems that can cause processing. Based on this, the feasibility of automatically and economically removing fluoride in wastewater (especially high-concentration fluoride wastewater) is further investigated. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 538006 A7 B7 V. Description of the invention (% invention 槪 沭 (please read the notes on the back before filling this page) An object of the present invention is to propose a system and method that continuously Remove fluoride from wastewater, while using calcium salt most appropriately and providing good filtering effect. Another object of the present invention is to propose a system and method that can be used for batch processing of fluoride and continuous treatment of irregular discharge. High-concentration fluoride wastewater and continuous treatment of wastewater with continuously changing high-concentration fluoride. According to the present invention, a method for removing fluoride from wastewater is proposed. This system includes a reaction tank to treat the wastewater by adding calcium salt, a filter tank to remove precipitated fluoride formed in the reaction tank, and a single fluoride electrode located at the first of the reaction tank. An input device is used to measure the fluoride concentration in the influent wastewater and provide an output signal, and a program-controllable controller is used to control the addition of the calcium salt to the reaction tank. The program-controllable controller defines the fluorine in the reaction tank The set point of the compound concentration is automatically controlled based on the set point and the output signal provided by a single fluoride electrode. The addition of calcium salts is automatically performed by the employee consumer cooperative of the Ministry of Economic Affairs and the Financial Affairs Bureau. In another embodiment of the present invention, the system includes a reaction The tank is used to treat the wastewater by adding calcium salt, the filter tank is used to remove the precipitated fluoride formed in the reaction tank, the first single fluoride electrode is located in the first input device of the reaction tank to measure the inflow Concentration of fluoride in wastewater and provides an output signal, a second single fluoride electrode located at the output device of the filter tank to detect the filtered wastewater Fluoride concentration and provides an output signal, and a controller may control program for controlling the addition of the calcium salt of the reaction vessel. The controller that can be controlled by this program defines the concentration of fluoride in the reaction tank. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -5- 538006 Μ B7 5. Description of the invention (3 points and based on the set point The output signals provided by the first and second single fluoride electrodes automatically control the addition of calcium salts (please read the precautions on the back before filling this page) This reaction tank is equipped with a ρ η sensor to determine the entry reaction The ρ 流入 of the inflow wastewater from the tank and provides an output signal. This P Η sensor is connected to the controller. This controller defines the P Η set point in the reaction tank and is based on the ρ Η set point and the output signal provided by the P Η sensor. Automatically control the addition of acid or alkaline solution. In one embodiment, the reaction tank includes at least one first, second, and third tank in series, and each tank is equipped with a P Η sensor to determine the P Η of each tank. Calcium salt is added to the first tank to a stoichiometric amount of 125%, and calcium salts added to the second and third tanks are 5 to 25% added to the first tank. Wisdom of the Ministry of Economic Affairs Consumption of property staff Another feature of the cooperative printed by the present invention is to propose a method for removing fluoride from wastewater. This method includes defining a fluoride concentration set point using a programmable controller and measuring the wastewater using a first single fluoride electrode. The concentration of fluoride in the water is automatically added to the calcium salt in the wastewater, the amount of which is based on the set point defined by the controller and the concentration of fluoride measured by the first single fluoride electrode, and a second single The fluoride electrode measures the concentration of fluoride in the effluent to ensure compliance with the discharge limits. Preferably, the amount of calcium salt added to the reaction tank is stoichiometric to 125% stoichiometry. This method can also include the use of a controller definition ρ Η set point and use of P 测定 sensor to measure ρ 废水 of waste water, and automatically add acid or alkaline solution to waste water, the amount of addition is based on the set point defined by the controller and ρ Η measured by ρ Η sensor This ρ I-I set point is set to be in the range of 6 to 9. The paper size is suitable for the Chinese National Standard (CNS) A4 specification (210 X 297 male) 7〇1 " 538006 A7 B7 Ministry of Economic Affairs Printed by the Intellectual Property Cooperatives Consumer Cooperative, V. Invention Description (4. A coagulant and / or flocculant can also be added to the wastewater to help remove the precipitated fluoride. Inflow into the wastewater to be treated by this method The concentration of fluoride contained can be changed continuously, from 50 to 10,000 PP m. The concentration of fluoride contained in the effluent treated by this method is as low as 2 to 10 ppm. The description and the scope of the attached patent application and the accompanying drawings will better understand other objects and advantages of the present invention. In the drawings: FIG. 1 is a system diagram of an embodiment of the present invention using a single fluoride electrode to remove fluoride from wastewater ; Figure 2 is the relationship between the stoichiometry of soluble fluoride and calcium at different P Η; Figure 3 is the stoichiometry of soluble fluoride and calcium at the different ρ η in the presence of N Η 4 + Relationship diagram; Figure 4 is a graph of fluoride emissions and fluoride concentration processed according to an embodiment of the present invention; Figure 5 is a fluoride discharge input and fluoride output processed according to another embodiment of the present invention Concentration map; Figure 6 It is a ρ Η diagram of a small amount of acid discharge control of about 7 cubic meters per hour according to an embodiment of the present invention; FIG. 7 is a relationship diagram between a system ρ Η and a very large amount of acid discharge according to an embodiment of the present invention; Figure 8 shows the paper size of the untreated wastewater before the treatment according to the present invention. The Chinese national standard (CNS) A4 specification (210X297 mm) 7γZ (please read the precautions on the back before filling this page) 538006 A7 B7 V. Description of the invention (3 Highly and fairly stable fluoride concentration map; Figure 9 is a graph showing the treatment results of the wastewater shown in Figure 8 according to the present invention; Figure 10 is a graph showing the results before the treatment according to the present invention. The treated wastewater varies considerably in fluoride concentration; FIG. 11 is a graph showing the treatment results of the wastewater shown in FIG. 10 according to the present invention. 10 System 15 Programmable controller 2 0 Reaction tank 2 1 Input device 2 2 Single fluoride electrode (Please read the precautions on the back before filling this page)
V1T 經濟部智慧財產局員工消費合作社印製 2 4 a 輸 入 裝 置 2 4 b 輸 入 裝 置 2 4 c 輸 入 裝 置 2 5 a 輸 入 裝 置 2 5 b 輸 入 裝 置 2 5 c 輸 入 裝 置 2 6 a P Η 感 知 器 2 6 b P Η 感 知 器 2 6 c P Η 感 知 器 3 1 反應 槽 3 2 反應 槽 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29?公釐） -8 - 538006 A7 B7 五、發明説明（$ 4 0 逆沖槽 4 2 輸入裝置 (請先閲讀背面之注意事項再填寫本頁) 5 0 濾槽 5 1 輸出裝置 52 單一氟化物電極 5 4 淤渣存放槽 5 5 濾膜 5 6 壓濾器 發明詳述 經濟部智慧財產局員工消費合作社印製 附圖1是根據本發明之移除廢水中之氟化物的系統 1 0之圖示。通常，系統1 〇包含反應槽2 0用以處理流 入的廢水，濾槽5 0用以移除在反應槽2 0中形成之任何 沉澱的氟化物，單一氟化物電極2 2 ,其位於反應槽2 0 的輸入裝置2 1以測定流入的廢水中之氟化物濃度及提供 輸出訊號，及程式可控制的控制器1 5，其回應單一氟化 物電極提供的輸出訊號地控制鈣鹽於反應槽2 0中之添加 ，單一氟化物電極5 2 ,其位於濾槽5 0的輸出裝置5 1 ，用以偵測排出之經處理的水中之氟化物濃度。 反應槽2 0包含輸出裝置2 1用以將流入的廢水引至 槽2 0中，和輸入裝置2 4 a用以將鈣鹽加至反應槽2 0 中以形成沉澱的氟化物。單一氟化物電極2 2 ,其位於反 應槽2 0的輸入裝置2 1以測定流入的廢水中之氟化物濃 度。單一氟化物電極2 2，與程式可控制的控制器1 5連 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -9 - 538006 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（》 接，此控制器定義氟化物濃度設定點。控制器1 5在單一 氟化物電極2 2的讀値高於控制器1 5的設定點時，自動 開始將鈣鹽加至反應槽2 0中。 反應槽2 0進行根據本發明之移除氟化物的第一個階 段，換言之，藉加至槽2 0的鈣鹽與流入之欲處理的廢水 中所含氟化物之反應而形成沉澱的氟化鈣，此如下面式子 所示者： C a + 2 + 2 F -> C a F 2 ( s ) ( 1 ) 附圖2顯示，於p Η二7 - 8時，使用略超過化學計 量的錦使得在流入的廢水中之即使超過1 〇 〇 〇 p p m氟 (F —)降至低於1 〇 p p m可溶解的氟（F —)。移除氟 化物的動力是氟化鈣（C a F 2 )極低的溶解度（K s p二 3 · 9x10 — 1A)。附圖2顯示於pH7時沉澱最完全 。添加超過化學計量的鈣可移除至低於溶解度限制1 6 ppm(CaF2)或8ppm(F_)。使用可溶解的鈣 鹽使得化學效用高於使用石灰漿料沉澱。石灰漿料鹼性高 且會形成沉澱氟化鈣的外殻及在漿料顆粒表面上的其他鹽 ，限制化學總效能。石灰漿料的反應慢得多。相較於幾乎 不溶解的鈣鹽（如：氧化鈣、氫氧化鈣和硫酸鈣），使用 氯化鈣和其他可溶性鈣鹽時，氟化鈣之形成和沉澱快得多 。較佳實施例中，P Η維持約4 — 6，以使得鈣維持迅速 反應的鈣離子（C a + 2 )形式。ρ η超過約6時，開始形 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ29?公餐) ~ (請先閱讀背面之注意事項再填寫本頁} 訂 538006 經濟‘部智慧財產局員工消費合作社印製 A7 B7五、發明説明（$ 成氫氧化鈣，沉澱反應變得效果較差，其效果與直接添力口 石灰漿料類似。 附圖3顯示沉澱化學亦可於有相當高量銨離子（如： 可能存在於緩衝的氧化物廢料中者，基本上超過5 0至 1 0 0 p P m )存在時進行。銨離子作爲鈣的錯合劑，延 緩氟化物沉澱，藉此使得相當大量的鈣離子用以提供完全 沉激效果。無論是否有銨離子存在，本發明的系統1 0將 可溶性氟化物含量降至低於典型半導體設備流出液的1 0 p p m限制。一旦建立程序，有機物（如：界面活性劑、 有機胺、聚合型穩定劑）和常用溶劑（如：異丙醇和丙酮 )不會影響氟化物移除。有必要調整鈣量以克服嫻於此技 藝者已知之分散劑潛在作用問題。根據本發明，以化學計 量至約1 2 5 %化學計量鈣沉澱氟化物。以使用5至1 0 %化學計量過量的鈣（C a + 2 )爲佳。 除非使用某些設備，否則氟化物的存在量通常低於排 放規定。這些幾克的小量排料容易操作。但有時會大量的 2 - 4公斤氟化物加工浸液排料。特別有利地，本發明之 系統1 0自動處理所有排料至低於1 0 p p m排放限制， 即使氟化物排料含大量酸性物質亦然。附圖4和5顯示以 本系統及方法處理兩種大量氟化物排料之的結果。爲淸晰 計，附圖4和5中的數據以對數座標表示，以顯現所達到 氟化物低輸出量效果。即使氟化物的輸入量是1 0 0 0 p p m ,本系統1 〇能夠使得輸出量達2 — 4 p p m。 附圖4和5中之約1 0 0 0 P p m的氟化物輸入量低 本紙張尺度適用中國國家榡準（CNS ) A4規格（210X 297公釐） -- (請先閱讀背面之注意事項再填寫本頁} 538006 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（$ 於實際値。氟化物電極讀値和進入廢水中之F ~真實量之間 的差異有數種原因。一個原因是使用離子交換電極作爲控 制感知器。如果所有的H F被離子化（僅發生於p Η 4 -6時），氟化物電極感知器僅讀取F —總量。持續調整在反 應槽2 0中的ρ Η以彌補低ρ Η輸入和C a F 2沉澱期間內 釋出的氫離子。同時，只要達到氟化物的設定點（基本上 是1 0至4 0 P p m )，系統1 〇立刻開始以F —滴定 C a + 2。最後，一些F —在沉澱之前就溢流離開反應槽 2 0到達下面所描述的額外反應槽3 1和3 2。本發明的 處理系統2 0將所有的因素列入考慮，以達到極低F —輸出 値，此示於附圖4和5。 再度參考附圖1，經處理的水之後通入濾槽5 0以移 除在反應槽2 0中形成之沉澱的氟化物。濾槽5 0以兩種 模式操作，即，濾槽操作模式和濾槽逆沖模式。操作模式 期間內，含氟化物沉澱物的廢水自濾槽5 0抽取通過膜 5 5。水溶液通過膜5 5時，氟化物沉澱顆粒不會通過而 是會累積在膜5 5的外表面。經過濾的”乾淨”水溢流離 開濾槽5 0頂部經由輸出裝置5 1丟棄或再利用。單一氟 化物電極5 2位於輸出裝置5 1以偵測氟化物濃度，以確 保排出之經過濾的水符合政府規定。逆沖模式期間內，濾 膜5 5被逆沖，使得經過濾的氟化物沉澱物自膜5 5外表 面掉落至濾槽5 0底部。收集經過濾的氟化物沉澱物並抽 至淤渣存放槽5 4，於此處將沉澱物濃縮至1至5 %固體 。欲使固體較緻密，濃縮的固體抽至壓濾器5 6，其可成 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12 - (請先閱讀背面之注意事項再填寫本頁) 訂 -.91. 538006 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（）〇 爲3 〇至9 0 %固體。此處，得以安全地丟棄無害的固體 〇 本發明的一個實施例中，基於控制器1 5定義的設定 點，控制器1 5自動控制鈣鹽之添加，以單一氟化物電極 2 2測定反應槽2 0中的氟化物濃度及以位於濾槽5 0輸 出裝置5 1處的單一氟化物電極5 2測定排放的水中之氟 化物濃度。 一個實施例中，濾槽5 0中的濾膜5 5通常是管狀” 套”構形。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。膜材料可購自市面多種來源，孔隙尺寸以在 〇 . 5微米至1 0微米範圍內爲佳，1微米最佳。通常， 濾槽5 0配備微濾膜5 5陣列。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）。已經 發現到此微濾膜處理的廢水通過0 . 5至1微米微濾膜的 流率可以在2 0 0 G F D至1 5 0 0 G F D範圍內。濾槽 50的操作壓力在3至15ps i (0 · 2 - 1 · 0大氣 壓）範圔內，膜每日通量在100-1000加侖/平方 英呎（或4 一 40立方米/平方米）範圍內（gfd)。 這些參數視膜數、它們的尺寸和流入的廢水濃度及流動而 改變。 -一個實施例中，p Η感知器2 6 a位於反應槽中以測 定進入該反應槽2 0之流入的廢水進料之P Η。此p Η感 知器2 6 a與控制器1 5 (其定義在反應槽2 0中的廢水 (請先閲讀背面之注意事項再填寫本頁) # 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（2】0X297公釐） -13 - 538006 Α7 Β7 五、發明説明（）1 (請先閱讀背面之注意事項再填寫本頁) p Η設定點）連接。輸入裝置2 5 a位於反應槽2 0處， 用以添加酸或鹼以調整反應槽2 0中的廢水P Η。控制器 1 5同步讀取Ρ Η感知器2 6 a的測得値並在讀値與控制 器2 0定義的設定點有差距時，自動控制酸或鹼溶液之添 加。 經濟部智慧財產局員工消費合作社印製 反應槽2 0中的廢水ρ Η控制在約6至9範圍內。此 ρ Η控制很重要。ρ Η過低會使得鈣鹽添加量提高（因爲 沉澱的氟化物會立刻再溶解，除非有過量的鈣存在）。 pH過高會引發氫氧化鈣沉澱，氫氧化鈣於低於ΡΗ7時 的再溶解緩慢，也會使得鈣鹽的添加量提高。工業廢水中 ，ρ Η變化頻繁，或者會因爲各種淸洗和程序槽排料而形 成穩定的低Ρ Η廢水流。藉ρ Η感知器2 6 a同步偵測反 應槽2 0中的廢水Ρ Η變化。在ρ Η感知器2 6 a的讀値 與控制器1 5的設定點有差異時，藉由自動添加酸或鹼溶 液，控制器1 5使得反應槽2 0中的廢水維持於Ρ Η設定 點。控制器1 5和設定點的確實電腦演算相當重要，其防 止回饋迴路、Ρ Η循環變動和化學品過度使用。不須要不 當的實驗，確實的電腦演算可由嫻於此技藝者進行程序控 制。基本上，各組設備依流率、在槽中的停留時間、預期 輸出量……等設計電腦演算。 Ρ Η感知器以根據廢水的ρ Η和氟化物濃度選擇爲佳 。一般Ρ Η電極迅速溶解於高度酸性和氟化物含量高的廢 水中。不會有因爲未對流入廢冰進行靈活的ρ Η控制，只 有對流出的廢水進行Ρ Η控制之添加大量石灰的傳統控制 -14- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） 538006 經濟部智慧財產局員工消費合作社印製 A7 ____ _B7__五、發明説明（）2 程序中之問題。較佳情況中，p Η感知器選自銻電極和特 別的耐氟化物玻璃ρ Η電極。最佳者是銻電極。 因爲添加大量鈣鹽及氟化鈣和副產物（如：矽酸鈣、 硫酸鈣、磷酸鈣、氟磷酸鈣、沉澱的有機聚合物（如：光 阻物殘渣）……等）迅速沉澱，所以可迅速測定Ρ Η和氟 化物感知電極。爲避免頻繁的人工淸潔，氟化物電極以自 身潔淨的氟化物感知電極爲佳。 附圖6顯示自動控制系統1 〇如何處理約7立方米/ 小時（3 0 g p in )的標準酸排料。週期性地大量酸排料 更難以控制。附圖7顯示系統與非常大量酸排料之關係。 大量排料相當於排出6 0升（1 6加侖）濃H C 1。這樣 的排料期間內，流率可由低於5至超過1 0立方米/小時 (低於2 2至超過4 4 g p m )，此使得ρ Η控制更加困 難。 一個實施例中，本系統1 0另包含逆沖槽4 0。此逆 沖槽4 0包含輸入裝置4 2以在來自反應槽2 0之經處理 的廢水中添加凝結劑和/或絮凝劑。氟化鈣（C a F 2 )沉 澱顆粒通常非常小且難以過濾。加至逆沖槽4 0中的凝結 劑趨使迅速水解反應以形成錯合的凝膠狀懸浮液和沉澱物 ，其吞沒和凝結氟化錦晶種顆粒和一些氟(陰離子以形成帶 有電荷的凝結附聚物。帶有相反電荷的聚合型絮凝劑加至 逆沖槽4 0中，破壞帶有電荷的凝結附聚物之穩定性而形 成聚合物橋連的附聚顆粒，其大至足以藉濾槽5 0中的膜 5 5有效過濾。就防止膜阻塞而言，界限明確的非黏著顆 本紙張尺度適用中國國家標準（ CNS ) A4規格（210X297公釐） -15 - (請先閱讀背面之注意事項再填寫本頁) 、11 538006 A7 ____ B7 _ 五、發明説明（）3 (請先閲讀背面之注意事項再填寫本頁) 粒是非常重要的。本發明中所用適當凝結劑和絮凝劑包括 EnChem0696 和 EnChem9025 聚合物（得自加州 Sunny vale 的 Microbar System) 〇 經濟部智慧財產局員工消費合作社印製 本發明的另一實施例中，基於欲處理的廢水流率，本 發明的系統1 〇以包含額外的二或多個反應槽3 1和3 2 爲佳。通常，反應槽3 1和3 2因爲以溢流槽形式操作， 所以比反應槽2 0來得小。反應槽3 1和3 2以包括與定 義這些槽的p Η設定點之控制器1 5連接的p Η感知器 26b和26c爲佳。輸入裝置24b和24c用於反應 槽3 1和3 2以藉由控制器1 5自動控制鈣鹽之添加。輸 入裝置2 5 b和2 5 c用以藉由控制器1 5自動控制地添 加酸或鹼以調整反應槽3 1和3 2中的p Η。此實施例中 ，反應槽3 1和3 2可具有效體積約3 0 0加侖，它們的 停留時間由約6至1 2分鐘。這些停留時間基於純塞流或 先進先出液流。確實流率由液流的標準混合和稀釋控制。 作爲轉運槽的槽3 2中之混合比反應槽2 0和3 1確實。 反應槽3 2在充滿時，每次取用至少1 〇 〇加侖地被靈活 抽取，以將氟化物經處理的廢水引至逆沖槽4 0中。 加至槽3 1和3 2的鈣視通過系統的總流率、槽2 0 中的氟化物總量、初Ρ Η、氨之存在和量、在各槽中的停 留時間及所欲流出的氟化物濃度而定。可約略計算這些添 加速率但以藉實驗設定爲佳。較佳情況中，加至槽3 i和 3 2的鈣量是加至反應槽2 0量之固定比。更佳情況中， 加至槽3 1和3 2的量是固定比例，由加至槽2 0中的量 -16- 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 538006 A7 B7_ 五、發明説明（）4 之5至2 5 %。 (請先閲讀背面之注意事項再填寫本頁) 因爲大部分的p Η調整於反應槽2 0中進行，所以通 常僅略爲調整槽3 1和3 2中的Ρ Η。附圖7中的數據顯 示本發明之系統1 0無視於反應槽2 0中的高度酸性，調 整反應槽3 1和3 2中之pH的效果。目前的軟體計算在 控制Ρ Η方面非常成功。用以移除氟化物，須要較窄的 Ρ Η範圍（6 — 9 )。用以移除砷，Ρ Η須控制於7 — 8 實驗 下列實例說明本發明之系統和方法，其用於氟化物之 分批處理；具不規則氟化物排料的廢水連續處理；及具連 續改變高含量氟化物的廢水之連續處理。本系統於電腦自 動控制下處理所有的這些方法。下列實驗僅作說明之用， 不欲限制本發明。 經濟部智慧財產局員工消費合作社印製 廢水以氯化鈣液、調整ρ Η的酸和鹼、EnChem0696和 EnChem9025凝結劑和絮凝劑之組合處理。氨和有機材料不 會干擾此方法。所用氯化鈣量視氟化物量、所欲氟化物排 出濃度及處理程序類型而定，與最後者的關係較不密切。 分批處理基本上使用約1 · 2 - 1 · 3莫耳鈣/ 2莫耳氟 化物。流動處理系統須要較大量，由約1 · 5 - 2莫耳鈣 / 2莫耳氟化物。EnChem0696的量基本上由約〇 · Οδ-Ο · 10 莫耳 / 升 （0 · 2— 0 · 4 毫升 / 加侖 ） ， EnChem062 5的量基本上由約〇 · 002 — 0 · 004莫耳 ϋ氏張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -17 - 538006 經濟部智慧財產局員工消費合作社印製 A7 _ B7 __五、發明説明（j5 /升（0 · 008 —〇· 016毫升/加侖），pH是7 一 8。 實例1 此實例說明本發明之系統和方法於氟化物之分批處理 。單一氟化物電極控制氟化鈣之滴定和沉澱，p Η感知器 控制氯化鈣之添加，降至事先定出的氟化物處理設定點。 較大量的氨須要略大量的氯化鈣，但本系統自動補足。類 似地，溶解的矽酸鹽' 磷酸鹽和高量硫酸鹽亦可與鈣反應 而形成不溶解的沉澱物。本方法自動添加足量鈣，以維持 氟化物處理設定點。附圖2所示者是1 0 0 0 p p. m廢水 分批處理的試驗結果。 實例2 此實例說明本發明之系統和方法，其用以連續處理具 不規則氟化物排料的廢水。就反應動力來看，於低p Η和 高氟化物和鈣濃度會較快，所以此常是最難處理的類型。 附圖4所示者是處理1 2立方米/小時（5 0 g pm)典 型設備排料的數據。廢水於處理之前的氟化物濃度高至 1 0 0 0 ρ p m，處理之後低於1 〇 ρ ρ ΙΏ。此實例中， 此系統由三個槽串聯構成。附圖4所示者是第一個輸入槽 中和來自處理系統之經最終過濾的廢水中之氟化物濃度。 實例3 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I 18 - —"~ (請先閲讀背面之注意事項再填寫本頁) 538006 A7 B7_ 五、發明説明（）6 (請先閲讀背面之注意事項再填寫本頁) 此實例說明本發明之系統和方法於連續處理具持續改 變高氟化物含量的廢水。這是處理系統最常見的類型。大 型設備通常已分離出帶有氟化物的廢液。此可能由來自淸 潔和沖洗之較低濃度的氟化物及來自加工浸液、管淸洗和 其他之較高濃度氟化物組成。本系統自動處理濃度變化範 圍寬廣的氟化物。可藉本系統處理的上限高至 10, 000ppm(10克/升）氟化物。本方法於高 濃度氟化物非常有效。因此不需將濃縮的廢料稀釋至低含 量。附圖8 - 1 1所示者是處理1 · 2立方米/小時（5 G P Μ )廢水流使其氟化物含量低於2 0 p p m的設備。 附圖8和1 0所示者是流入的廢水中的氟化物，其中，附 圖8是廢水氟化物濃度高且相當穩定的一日，附圖1 〇是 廢水變化大且一日開始和終了時之氟化物濃度低的一曰。 經濟部智慧財產局員工消費合作社印製 此氟化物處理系統由三個槽串聯構成。附圖9和1 1 所示者是第一個輸入槽和來自處理系統之最終經過濾的廢 水之氟化物濃度。此系統中，第一個輸入槽中的氟化物處 理設定點是4 0 p p m。無論輸入的廢水濃度如何，只要 其高於40 ppm,就可以自動處理降至40ppm。磷 酸鹽、矽酸鹽和硫酸鹽不會干擾。在額外槽中進行進一步 處理，以達到所欲流出氟化物濃度。 本發明的一個優點是降低移除氟化物之成本。僅使用 一個輸入和輸出氟化物感知電極、一或多個反應槽和相關 電腦以有效軟體精確控制p Η和氟化物的可程式控制的控 制器，就可藉簡化且有效控制系統達成此目的。節制成本 -19- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） 538006 A7 _B7____ 五、發明説明（丨7 源自於使用較少量鈣化學品、因爲更精確的P Η控制而使 用較少的酸和鹼、產生的淤渣較少而降低拋棄成本，因爲 形成的淤渣較少而使得過濾更快也更容易，因爲感知器數 目較少而降低維護成本..等。另一優點在於所有的氟化 物移除步驟在電腦控制下自動進行，藉此免除了大部分的 操作疏失。 本發明之特定實施例和實例的前述描述僅用以說明和 描述，雖然已藉前面的一些實例說明本發明，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 發明之範圍含括此處所述一般範圍及所附申請專利範圍及 它們的對等情況。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慈財產局員工消費合作社印製 -20- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐）V1T Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 2 4 a Input device 2 4 b Input device 2 4 c Input device 2 5 a Input device 2 5 b Input device 2 5 c Input device 2 6 a P 感知 Sensor 2 6 b P Η Perceptron 2 6 c P Η Perceptron 3 1 Reaction tank 3 2 Reaction tank The paper size applies the Chinese National Standard (CNS) A4 specification (210X29? mm) -8-538006 A7 B7 V. Description of the invention ($ 4 0 Backwash tank 4 2 Input device (please read the precautions on the back before filling out this page) 5 0 Filter tank 5 1 Output device 52 Single fluoride electrode 5 4 Sludge storage tank 5 5 Filter membrane 5 6 Invention of filter press Detailed description Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Figure 1 is a diagram of a system 10 for removing fluoride in wastewater according to the present invention. Generally, the system 10 includes a reaction tank 20 for processing inflows Wastewater, filter tank 50 is used to remove any precipitated fluoride formed in the reaction tank 20, a single fluoride electrode 22, which is located in the input device 21 of the reaction tank 20 to determine the fluorine in the incoming wastewater The concentration of the substance and the output signal provided, and the program-controllable controller 15 control the addition of the calcium salt to the reaction tank 20 in response to the output signal provided by the single fluoride electrode, and the single fluoride electrode 5 2 is located in the filter The output device 51 of the tank 50 is used to detect the concentration of fluoride in the discharged treated water. The reaction tank 20 includes the output device 21 for introducing the influent wastewater into the tank 20 and the input device 2. 4a is used to add calcium salt to the reaction tank 20 to form precipitated fluoride. A single fluoride electrode 22 is located in the input device 21 of the reaction tank 20 to determine the fluoride concentration in the influent wastewater. Single fluoride electrode 2 2 and program-controllable controller 1 5 This paper size is applicable to Chinese National Standard (CNS) A4 (210X 297 mm) -9-538006 Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperative Printed A7 B7 V. Explanation of the invention ("Then, this controller defines the set point of fluoride concentration. When the reading of single fluoride electrode 22 is higher than the set point of controller 15, it automatically starts to add calcium salt. Into the reaction tank 20 20 to carry out the first stage of fluoride removal according to the invention, in other words, to form precipitated calcium fluoride by reacting the calcium salt added to the tank 20 with the fluoride contained in the wastewater to be treated, This is shown by the following formula: C a + 2 + 2 F-> C a F 2 (s) (1) Figure 2 shows that when p Η 2 7-8 is used, slightly more than stoichiometric It can reduce the fluorine (F —) in the inflowing wastewater to less than 10 ppm soluble fluorine (F —) even if it exceeds 1000 ppm. The motivation for removing fluoride is the extremely low solubility of calcium fluoride (C a F 2) (K s p 2 3 · 9x10 — 1A). Figure 2 shows that precipitation is most complete at pH 7. Addition of more than stoichiometric calcium can be removed below the solubility limit by 16 ppm (CaF2) or 8 ppm (F_). The use of soluble calcium salts results in higher chemical utility than precipitation with lime slurry. The lime slurry is highly alkaline and will form a shell of precipitated calcium fluoride and other salts on the surface of the slurry particles, limiting the overall chemical efficiency. The reaction of the lime slurry is much slower. Compared to almost insoluble calcium salts (such as: calcium oxide, calcium hydroxide, and calcium sulfate), calcium chloride and other soluble calcium salts use calcium fluoride to form and precipitate much faster. In a preferred embodiment, P Η is maintained at about 4 to 6, so that calcium maintains a rapidly reacting form of calcium ions (C a + 2). When ρ η exceeds about 6, the size of the original paper is applicable to the Chinese National Standard (CNS) Α4 specification (210 × 29? Meal) ~ (Please read the precautions on the back before filling this page) A7 B7 printed by the consumer cooperative V. Description of the invention ($ to calcium hydroxide, the precipitation reaction becomes less effective, and its effect is similar to that of directly adding a lime slurry. Figure 3 shows that precipitation chemistry can also have a relatively high amount of ammonium Ions (such as: those that may be present in buffered oxide waste, basically more than 50 to 100 p P m). Ammonium ions act as a calcium complexing agent to delay the precipitation of fluoride, thereby making a considerable amount The calcium ion is used to provide a complete stimulating effect. Regardless of the presence of ammonium ions, the system 10 of the present invention reduces the soluble fluoride content below the 10 ppm limit of a typical semiconductor device effluent. Once a program is established, the organic ( Such as: surfactants, organic amines, polymeric stabilizers) and common solvents (such as isopropanol and acetone) will not affect the removal of fluoride. It is necessary to adjust the amount of calcium to overcome Potential effects of dispersants known to the artisan. According to the present invention, fluoride is precipitated from stoichiometry to about 125% stoichiometric calcium. It is preferred to use 5 to 10% stoichiometric excess of calcium (C a + 2). Unless certain equipment is used, the amount of fluoride present is usually lower than the emission regulations. These small grams of discharge are easy to handle. But sometimes a large amount of 2 to 4 kg of fluoride processing immersion discharge is particularly advantageous. Ground, the system 10 of the present invention automatically processes all discharges to below 10 ppm emission limit, even if the fluoride discharge contains a large amount of acidic substances. Figures 4 and 5 show that the system and method are used to process two large amounts of fluorine. The results of compound discharge. For clarity, the data in Figures 4 and 5 are expressed in logarithmic coordinates to show the effect of low output of fluoride achieved. Even if the input of fluoride is 100 ppm, the System 10 can achieve an output of 2-4 ppm. Figures 4 and 5 show a low fluoride input of about 1 00 P pm. This paper is sized for China National Standards (CNS) A4 (210X 297 mm) %)-(Please read the notes on the back first Refill this page} 538006 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention description ($ in actual volume). There are several reasons for the difference between the actual reading of the fluoride electrode and the amount of F to enter the wastewater. One reason is to use an ion exchange electrode as the control sensor. If all HF is ionized (only occurs at p 4 -6), the fluoride electrode sensor only reads F-total. Continuous adjustment in reaction tank 2 Ρ 中 in 0 to compensate for the low ρ Η input and the hydrogen ions released during the precipitation of Ca F 2. At the same time, as long as the set point of the fluoride is reached (basically 10 to 40 P pm), the system 1 〇 Immediately start titrating C a + 2 with F —. Finally, some F—overflow leaves the reaction tank 20 before settling to the additional reaction tanks 31 and 32 described below. The processing system 20 of the present invention takes all factors into consideration to achieve an extremely low F-output 値, which is shown in Figures 4 and 5 of the accompanying drawings. Referring again to FIG. 1, the treated water is then passed into a filter tank 50 to remove the precipitated fluoride formed in the reaction tank 20. The filter tank 50 is operated in two modes, that is, a filter tank operation mode and a filter tank reverse mode. During operation mode, wastewater containing fluoride deposits is drawn from the filter tank 50 through the membrane 55. When the aqueous solution passes through the membrane 55, the fluoride precipitate particles do not pass through but accumulate on the outer surface of the membrane 55. The filtered "clean" water overflows from the top of the filter tank 50 and is discarded or reused through the output device 51. A single fluoride electrode 5 2 is located at the output device 51 to detect the fluoride concentration to ensure that the filtered water discharged meets government regulations. During the backflush mode, the filter membrane 55 was backflushed, so that the filtered fluoride precipitate fell from the outer surface of the membrane 55 to the bottom of the filter tank 50. The filtered fluoride precipitate was collected and pumped to a sludge storage tank 54 where it was concentrated to 1 to 5% solids. If you want to make the solids more dense, the concentrated solids will be pumped to the pressure filter 5 6. The applicable paper size is China National Standard (CNS) A4 (210X297 mm) -12-(Please read the precautions on the back before filling this page ) Order-.91. 538006 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention () 0 is 30 to 90% solids. Here, the harmless solids can be safely discarded. In one embodiment of the present invention, the controller 15 automatically controls the addition of calcium salts based on a set point defined by the controller 15 and measures the reaction tank with a single fluoride electrode 22 The concentration of fluoride in 20 and the concentration of fluoride in the discharged water were measured with a single fluoride electrode 52 located at the output device 51 of the filter tank 50. In one embodiment, the filter membrane 55 in the filter tank 50 is generally in a tubular "sleeve" configuration. The sleeve is placed on a narrow carrier tube to prevent the sleeve from disintegrating during use. Membrane materials can be purchased from a variety of sources in the market. The pore size is preferably in the range of 0.5 micrometers to 10 micrometers, and 1 micrometer is the best. Generally, the filter tank 50 is equipped with a microfiltration membrane 55 array. The sleeve is placed on a long and narrow carrier tube to prevent the sleeve from disintegrating during use. To achieve high flow rates and throughput, multiple membranes or membrane groups can be used (each with multiple filter sleeves). It has been found that the flow rate of the wastewater treated by this microfiltration membrane through the 0.5 to 1 micron microfiltration membrane can be in the range of 200 G F D to 150 G F D. The operating pressure of the filter tank 50 is within the range of 3 to 15 ps i (0 · 2-1 · 0 atmosphere), and the daily membrane flux is 100-1000 gallons per square foot (or 4 to 40 cubic meters per square meter). Within range (gfd). These parameters vary depending on the number of membranes, their size and the concentration and flow of incoming wastewater. -In one embodiment, the p Η sensor 2 6 a is located in the reaction tank to determine the P Η of the influent wastewater feed entering the reaction tank 20. The p Η sensor 2 6 a and the controller 15 (the waste water defined in the reaction tank 20 (please read the precautions on the back before filling this page) # The paper size is applicable to the Chinese National Standard (CNS) A4 Specifications (2) 0X297 mm -13-538006 Α7 Β7 V. Description of the invention () 1 (Please read the notes on the back before filling this page) p ΗSetpoint) connection. The input device 25a is located at the reaction tank 20, and is used to add acid or alkali to adjust the wastewater PP in the reaction tank 20. The controller 1 5 reads the measured value of the P sensor 2 6 a synchronously and automatically controls the addition of the acid or alkali solution when the reading is different from the set point defined by the controller 20. The waste water ρ 印 in the reaction tank 20 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is controlled within a range of about 6 to 9. This ρ Η control is important. Too low ρ will increase the amount of calcium salt added (because the precipitated fluoride will be redissolved immediately unless there is an excess of calcium). Excessive pH will cause precipitation of calcium hydroxide, and slow re-dissolution of calcium hydroxide below pH 7 will also increase the amount of calcium salt added. In industrial wastewater, ρ 频繁 changes frequently, or a stable low-P Η wastewater stream is formed due to various washing and process tank discharges. The change in the wastewater P Η in the reaction tank 20 is detected synchronously by the ρ Η sensor 2 6 a. When the reading of the ρ Η sensor 2 6 a differs from the set point of the controller 15, by automatically adding an acid or alkali solution, the controller 15 keeps the wastewater in the reaction tank 20 at the Η set point . The exact computer calculation of the controller 15 and the setpoints is very important to prevent feedback loops, cyclic fluctuations and excessive use of chemicals. There is no need for improper experiments. The actual computer calculations can be controlled by those skilled in the art. Basically, each group of equipment is designed with computer calculations based on flow rate, residence time in the tank, expected output ... The P Η sensor is preferably selected according to the ρ Η and fluoride concentration of the wastewater. Generally, the Pd electrode is rapidly dissolved in waste water with high acidity and high fluoride content. There will not be the traditional control of adding a large amount of lime because there is no flexible ρ control for the inflow of waste ice, but only for the effluent control of effluent wastewater. -14- This paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210 × 297) (Mm) 538006 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ____ _B7__ V. Invention Description (2) Problems in the procedure. Preferably, the p Η sensor is selected from an antimony electrode and a special fluoride-resistant glass ρ Η electrode. The best is an antimony electrode. Because a large amount of calcium salt and calcium fluoride and by-products (such as: calcium silicate, calcium sulfate, calcium phosphate, calcium fluorophosphate, precipitated organic polymers (such as photoresist residues), etc.) are rapidly precipitated, so Rapid measurement of P Η and fluoride sensing electrodes. To avoid frequent manual cleaning, it is better to use a clean fluoride sensing electrode. Figure 6 shows how the automatic control system 10 processes a standard acid discharge of about 7 cubic meters per hour (30 g p in). Periodically large acid discharges are more difficult to control. Figure 7 shows the relationship of the system to a very large amount of acid discharge. A large amount of discharge is equivalent to discharging 60 liters (16 gallons) of concentrated H C 1. During such a discharge period, the flow rate can be from less than 5 to more than 10 cubic meters / hour (below 22 to more than 4 4 g p m), which makes ρ Η control more difficult. In one embodiment, the present system 10 further includes a backwash groove 40. This backwash tank 40 contains an input device 42 to add a coagulant and / or flocculant to the treated wastewater from the reaction tank 20. Calcium fluoride (C a F 2) precipitate particles are usually very small and difficult to filter. The coagulant added to the backwash tank 40 tends to undergo a rapid hydrolysis reaction to form incompatible gel-like suspensions and precipitates, which engulf and coagulate the fluorinated bromide seed particles and some fluorine (anions to form a charged charge). Agglomerated agglomerates. Polymeric flocculants with opposite charges are added to the backwash tank 40, which destroys the stability of the charged agglomerates and forms polymer-bridged agglomerates, which are as large as It is enough to effectively filter by the membrane 5 5 in the filter tank 50. In terms of preventing the membrane from blocking, the non-adhesive particles with clear boundaries are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -15-(please first Read the notes on the back and then fill out this page), 11 538006 A7 ____ B7 _ V. Description of the invention () 3 (Please read the notes on the back before filling out this page) Granules are very important. Appropriate coagulants used in the present invention And flocculants include EnChem0696 and EnChem9025 polymers (available from the Microbar System in Sunny vale, California). Printed by the Consumers ’Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs. In another embodiment of the present invention, based on the wastewater flow rate to be treated, The invented system 10 preferably contains additional two or more reaction tanks 31 and 32. Generally, reaction tanks 31 and 32 are smaller than reaction tank 20 because they operate as overflow tanks. Reaction The slots 3 1 and 3 2 preferably include p Η sensors 26b and 26c connected to the controller 15 which defines the p Η set points of the slots. Input devices 24b and 24c are used to respond to the slots 3 1 and 32 to thereby The addition of calcium salt is automatically controlled by the controller 15. The input devices 2 5 b and 2 5 c are used to automatically control the addition of acid or alkali by the controller 15 to adjust p Η in the reaction tanks 3 1 and 32. In this embodiment, the reaction tanks 31 and 32 may have an effective volume of about 300 gallons, and their residence time ranges from about 6 to 12 minutes. These residence times are based on pure plug flow or first-in-first-out liquid flow. True flow The rate is controlled by the standard mixing and dilution of the liquid stream. The mixing ratio in tank 32 as the transfer tank is determined by reaction tanks 20 and 31. When tank 32 is full, at least 100 gallons are taken each time. Flexible extraction to direct fluoride treated wastewater to backflush tank 40. Calcium added to tanks 3 1 and 32 2 depends on the total flow rate through the system, It depends on the total amount of fluoride in 20, the initial pH, the presence and amount of ammonia, the residence time in each tank, and the concentration of fluoride to flow out. These addition rates can be roughly calculated, but it is better to use experimental settings. In a preferred case, the amount of calcium added to the tanks 3 i and 32 is a fixed ratio of the amount added to the reaction tank 20. In a more preferred case, the amount of calcium added to the tanks 3 1 and 32 is a fixed ratio. Amount in slot 20 0-16- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) 538006 A7 B7_ 5. Description of invention (5) 5 to 25%. (Please read the notes on the back before filling out this page.) Because most p Η is adjusted in reaction tank 20, usually only slightly adjust Ρ in tanks 3 1 and 32. The data in FIG. 7 shows the effect of the system 10 of the present invention to adjust the pH in the reaction tanks 31 and 32 regardless of the high acidity in the reaction tank 20. Current software calculations have been very successful in controlling PQ. For the removal of fluoride, a narrower range of pH is required (6-9). To remove arsenic, PΡ must be controlled at 7-8. The following examples illustrate the system and method of the present invention for batch processing of fluorides; continuous treatment of wastewater with irregular fluoride discharge; and continuous Continuous treatment of wastewater with high fluoride content. This system handles all of these methods under the computer's automatic control. The following experiments are for illustration purposes only and are not intended to limit the invention. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Wastewater is treated with a combination of calcium chloride solution, acid and alkali adjusted ρ 、, EnChem0696 and EnChem9025 coagulant and flocculant. Ammonia and organic materials do not interfere with this method. The amount of calcium chloride used depends on the amount of fluoride, the desired fluoride emission concentration, and the type of treatment program, and is less closely related to the last. Batch processing basically uses about 1.2-1.3 moles calcium / 2 moles fluoride. The flow handling system requires a larger amount, consisting of approximately 1.5-2 mol calcium / 2 mol fluoride. The amount of EnChem0696 is basically about 0.005-0 · 10 Moore / liter (0 · 2-0 · 4 ml / gallon), the amount of EnChem062 5 is basically about 0.002-0 · 004 Moore's Zhang scale is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) -17-538006 Printed by A7 _ B7 __ of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (j5 / liter (0 · 008 —〇 · 016 ml / gallon), pH is 7 to 8. Example 1 This example illustrates the batch processing of fluoride in the system and method of the present invention. A single fluoride electrode controls the titration and precipitation of calcium fluoride, and p Η sensor control The addition of calcium chloride is reduced to a predetermined fluoride treatment set point. A larger amount of ammonia requires a slightly larger amount of calcium chloride, but this system automatically makes up for it. Similarly, dissolved silicate 'phosphates and high amounts Sulfate can also react with calcium to form an insoluble precipitate. This method automatically adds a sufficient amount of calcium to maintain the set point for fluoride treatment. The one shown in Figure 2 is the batch processing of 1 0 0 0 p p. M wastewater Experimental results. Example 2 This example illustrates the system of the present invention. The system and method are used to continuously treat wastewater with irregular fluoride discharge. From the perspective of reaction kinetics, low p Η and high fluoride and calcium concentrations will be faster, so this is often the most difficult type to handle. Figure 4 shows the discharge data of a typical equipment for processing 12 cubic meters per hour (50 g pm). The fluoride concentration of the wastewater before the treatment is as high as 1 0 0 0 ρ pm, and it is lower than 1 0 after the treatment. ρ ρ ΙΏ. In this example, the system consists of three tanks in series. The one shown in Figure 4 is the fluoride concentration in the first input tank and in the final filtered wastewater from the treatment system. Example 3 This paper Standards are applicable to China National Standard (CNS) A4 specifications (210X297 mm) I 18-— " ~ (Please read the precautions on the back before filling this page) 538006 A7 B7_ V. Description of the invention () 6 (Please read the back first (Please note this page before filling out this page) This example illustrates the system and method of the present invention for continuous treatment of wastewater with continuously changing high fluoride content. This is the most common type of treatment system. Large-scale equipment has usually been separated with fluoride. Waste liquid. This may be caused by Self-cleaning and rinsing of the lower concentration of fluoride and the higher concentration of fluoride from processing immersion solution, tube cleaning and other. This system automatically handles fluorides with a wide range of concentration changes. The upper limit that can be processed by this system Up to 10,000 ppm (10 g / l) of fluoride. This method is very effective at high concentrations of fluoride. Therefore, it is not necessary to dilute the concentrated waste to a low level. Figure 8-1 1 shows treatment 1 · 2 Equipment with a cubic meter per hour (5 GP M) wastewater stream with a fluoride content below 20 ppm. Figures 8 and 10 show the fluoride in the influent wastewater. Among them, Figure 8 is a day when the concentration of fluoride in the wastewater is high and quite stable. Figure 10 is a day when the wastewater changes greatly and the day starts and ends. The time when the fluoride concentration is low. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This fluoride treatment system consists of three tanks connected in series. Figures 9 and 11 show the fluoride concentration of the first input tank and the final filtered waste water from the treatment system. In this system, the fluoride treatment setpoint in the first input tank is 40 p p m. Regardless of the input wastewater concentration, as long as it is higher than 40 ppm, it can be automatically reduced to 40 ppm. Phosphates, silicates and sulfates do not interfere. Further processing is performed in additional tanks to achieve the desired effluent fluoride concentration. One advantage of the present invention is the reduced cost of fluoride removal. This can be achieved by simplifying and effectively controlling the system using only one input and output fluoride sensing electrode, one or more reaction tanks and associated computers with effective software to accurately control the pΗ and fluoride programmable controllers. Cost-effectiveness-19- This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 538006 A7 _B7____ V. Description of the invention (丨 7 comes from the use of a smaller amount of calcium chemicals because of the more accurate P Η Η Control and use less acid and alkali, less sludge generated and reduce the cost of disposal. Because less sludge is formed, filtration is faster and easier, and maintenance costs are reduced because of fewer sensors .. etc. Another advantage is that all the fluoride removal steps are performed automatically under computer control, thereby avoiding most of the operational mistakes. The foregoing description of specific embodiments and examples of the present invention is for illustration and description only, although borrowed The foregoing examples illustrate the present invention, and the present invention is not limited thereto. It is not intended to limit the present invention to the specific forms disclosed herein. Obviously, many modifications, embodiments, and changes can be made from the foregoing experience. It is hoped that the scope of the present invention includes The general scope described here and the scope of the attached patent applications and their equivalents. (Please read the notes on the back before filling out this page) Bureau employees consumer cooperatives printed -20- This paper scales applicable Chinese National Standard (CNS) Α4 Specification (210X 297 mm)