經濟部智慧財產局員工消費合作社印製 548243 A7 ___B7____ 五、發明説明（2 ) 用水中之砷爲優先處理污染物。1 9 7 4年以後’美國環 保署（E P A )制訂飮用水中最大污染物標準（M C L ) 砷含量爲50PPb ( = /zg/L)。根據屬於與人口健 康危害關聯曝露於飮用水中之高濃度砷之最近發現結果’ 美國環保署（E P A )薦請降低最大污染物標準（M C L )砷含量從50ppb到2ppb。它可預期的是單在美 國，超過1 2，0 0 0個公共用水事業單位將無法達到此 更嚴厲的建議砷標準。一個順從建議砷標準2 P P b之成 本位數估計爲一年超過五十億美元。 美國私有井無法達到現存的飮用水中最大污染物標準 (MC L )砷含量爲5 0 P P b或建議的最大污染物標準 (MCL)砷含量2ppb者之數目，並不知道。相信美 國許多地方，有數千生產飮用水之私有井被砷所污染，因 而賴以此自產水爲生之家庭，導致潛在的嚴重健康危害。 此外，飮用水區域地高濃度砷污染是全球性的問題。 例如在西孟加拉及印度，估計有2 0 0，0 0 〇人目前遭 受到砷誘因之皮膚病害，其中一些已然經趨近先期癌症的 過角質化症（hyperkeratoses )。因此，由水溶液諸如飲用 水及/或廢水中移除砷之系統及方法，是高度重要的。 另一個重要的問題爲水溶液諸如飮用水及/或廢水中 出現氟化物。對人類而言，曝露於飮用水中氟化物之濃度 高於1 p p m是有毒的。此外，帶有氟化物之水能影響植 物及野生動物之變壞。 工業製程，特別是那些使用在半導體之製造者，爲含 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） " ' ---~ -5- (請先閲讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 548243 A7 ___B7____ V. Description of the invention (2) Arsenic in water is used as a priority treatment pollutant. After 1974, the US Environmental Protection Agency (EPA) formulated the maximum pollutant standard (M C L) in tritium water with an arsenic content of 50 PPb (= / zg / L). According to the recent findings of high concentrations of arsenic exposed to radon water in association with population health hazards, the US Environmental Protection Agency (EPA) recommends lowering the maximum pollutant standard (MCL) arsenic content from 50ppb to 2ppb. It is expected that in the United States alone, more than 12,000 public water utilities will fail to meet this more stringent recommended arsenic standard. The cost of a compliant arsenic standard 2 P P b is estimated to be more than $ 5 billion a year. Private wells in the United States are not able to meet the existing maximum pollutant standard (MC L) arsenic content of 50 ppm in the tritium water or the recommended maximum pollutant standard (MCL) arsenic content of 2 ppb, it is unknown. It is believed that in many parts of the United States, thousands of private wells producing tritium water are contaminated with arsenic, and families relying on this self-produced water for their livelihoods cause potentially serious health hazards. In addition, the high concentration of arsenic pollution in tritium water areas is a global problem. For example, in West Bengal and India, an estimated 20,000 people are currently suffering from arsenic-induced skin diseases, some of which are already approaching hyperkeratoses of advanced cancer. Therefore, systems and methods for removing arsenic from aqueous solutions such as drinking water and / or wastewater are highly important. Another important issue is the presence of fluoride in aqueous solutions such as tritium water and / or wastewater. To humans, fluoride concentrations in water exposed to radon above 1 p p m are toxic. In addition, fluoride-containing water can affect the deterioration of plants and wildlife. Industrial processes, especially those used in semiconductors, apply the Chinese National Standard (CNS) A4 specification (210X297 mm) for this paper size " '--- ~ -5- (Please read the notes on the back first (Fill in this page again)
548243 A7 B7 五、發明説明（3 ) 有氟化物及砷等兩者廢水之來源。尤其是通常使用在電信 工業從砷化鎵製造的裝置爲廢水中可溶性砷之重要來源。 在半導體受質的砷原子之離子佈植爲另一來源。含有氟化 物的化學藥品通常是使用於蝕刻受質，與淸潔材料及伴隨 加工設備上，其兩者均會將氟化物導入廢水中。 砷原子以四種價狀態存在（亦稱氧化狀態）；即 —3、0、+ 3及+ 5價。標準狀況下，+ 3及+ 5價狀 態各別發現爲如A s〇3 — 3 (亞砷酸鹽）及A s〇4 1 ( 砷酸鹽）離子。爲以凝聚作用有效的移除砷，砷應該是以 + 5價氧化狀態，較佳者爲砷酸鹽形態。亞砷酸鹽則以諸 如吸收及凝聚技術作部分地移除，但是該機制是低有效性 ，因爲它的主要形態一亞砷酸（Η 3 A s〇3 )是弱酸（ p K a 1約9 _ 2 3 )，殘餘在其P Η値未離子化的其經 由吸收移除最爲有效；即在5〜8範圍。相反地，〇 -砷 酸（Η 3 A s〇4，砷是以+ 5價氧化狀態）是強酸（ p K a 1約2 · 2 0 )，係從P Η値約2開始之離子形態 。負電荷形態對吸收及凝聚最爲有效。 許多習知技術曾經應用在從廢水中移除砷。例如諸如 共同沈澱、氧化鋁吸附及古典的以陰離子樹脂之離子交換 等均曾被使用過。該技術達成有限的成就，且限制其移除 效率僅約9 5 %。較新的技術曾經開發，例如 US Patent No. 5,3 68,703揭示使用電化學電池，其在電化學 上產生亞鐵離子。一溫和的氧化條件以添加過氧化物建立 之，其能氧化亞鐵離子成鐵離子，因而形成氫氧化鐵。然 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公着)' " -- (請先閲讀背面之注意事項再填寫本頁) •裝. 訂 經濟部智慧財產局員工消費合作社*S衾 -6- 548243 A7 B7_ 五、發明説明（4 ) (請先閱讀背面之注意事項再填寫本頁) 後使用氫氧化鐵移除砷。另一習知技術爲描述於 US Patent No. 5,908,557者其三價的砷氧化成五價的砷，然 後以含有N -烷基吡啶之吸附介質移除。該較新的技術可 提供移除效率的改進，但是該等技術是麻煩的，需要特別 的設備及/或特性化學藥品，且不易安裝或操作，尤其是 私有井水處理爲然。 氟化物之移除技術，包括使用鈣及其他化合物，以單 一或多階段處理程序沈澱氟化物，諸如描述於 US Patent No. 4，145,282、· 5,04 3,07 2 及.5,403,495。該等技 術移除效率有些變化，且不能應對氟化物之移除與砷的移 除在一起。 因此’提供一種能夠由水溶液尤其是飮用水或工業廢 水中，同時移除砷及氟化物至安全標準之系統及方法，將 會是高度期待的。爲應對各色各樣的工業用水需求、大都 市公共用水、私有井水等，及在開發及未開發中國家兩者 用水’更期望該系統及方法會是具通融性及充分健全的。 經濟部智慧財產局員工消費合作'吐印製 發明之槪述： 因此’本發明之目的爲提供由水溶液，特別是飮用水 或廢水中同時移除砷及氟化物之改進系統及方法。更明確 地說’本發明者發現使用某些鹽類預處理及保持水溶液在 一定的p Η値範圍，由水溶液中同時移除砷及氟化物之新 糸統及方法。 普通，本發明提烘由水溶液中同時移除砷及氟化物之 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -7- 548243 Α7 Β7 經濟部智1財產局工消費合作.11^¾ 五、發明説明（5 ) 系統及方法，包括+ 5價氧化狀態之砷（亦可能出現+ 3 價氧化狀態）及氟化物（游離氟化物陰離子），其特徵爲 水溶液係在p Η値爲5〜8之範圍，用鈣鹽及鐵鹽或鋁鹽 之組合物處理，形成帶有砷及氟化物之沈澱物或固體。然 從水溶液中過濾此等固體後，因而移除砷及氟化物。 另一方面，本發明提供由水溶液中同時移除砷及氟化 物之系統及方法，包含 下列步驟：提供一種包括砷酸鹽離子形態的砷及氟化 物之水溶液。水溶液之ρ Η値調節到5〜8之範圍。水溶 液之ρ Η値高於8時移除砷的效力是大爲降低。將鈣鹽加 入水溶液中以促進氟化物之沈澱形成帶有氟化物之粒子或 絮凝物。然後將鐵或鋁爲底質的鹽類加入水溶液中。鐵或 鋁爲底質的鹽類形成金屬氫氧化物絮凝物或懸浮物，其吸 收帶有砷酸鹽離子及氟化物之粒子而形成帶有砷及氟化物 之固體。然後由水溶液中移除帶有砷及氟化物之固體。 本發明另一方面，提供一種系統，包含第一反應槽供 收受包括砷及氟化物之水溶液。水溶液之ρ Η値調節到5 〜8之範圍，且將第一注入裝置耦合於第一反應槽而將鈣 鹽注入水溶液中。第一混合器較佳者耦合於第一反應槽供 水溶液混合之用，以促進氟化物之沈澱形成帶有氟化物之 粒t。桌一反應槽提供收受從第一反應槽之水溶液，其中 水溶液之Ρ Η値視需要再調節、維持在5〜8之範圍。將 第二注入裝置耦合於第二反應槽而將鐵或鋁爲底質的鹽類 注入水溶液中。較佳者第二混合器耦合於第二反應槽供水 (讀先閱讀背面之注意事項再填寫本頁) .裝· 訂--*-- ^ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公楚） -8- 548243 Α7 Β7 五、發明説明（6 ) (請先閱讀背面之注意事項再填寫本頁) 溶液及鹽類混合，形成金屬氫氧化物絮凝物或懸浮物，其 吸收帶有砷離子及氟化物之粒子，而形成帶有砷及氟化物 之固體。提供過濾系統以移除固體，及包括具有一個或更 多過濾膜配置成管狀襪套組態之一個或更多過濾容器，且 適置於細溝管及一個或更多沈降槽。 圖式簡要說明： 讀過本發明詳細描述，本發明其他目的及優點將會變 成顯而易見的。而參考圖解增補申請提供如下，其中·· 圖1 :顯示ρ Η値作爲函數之砷酸鹽及亞砷酸鹽吸收 率圖。 圖2 ··根據本發明之系統及方法中一個實施例的處理 系統方塊圖。 圖3 :顯示根據本發明之氟化物濃度圖。 圖4 :圖解根據本發明之砷濃度圖。 主要元件對照表 經濟部智慧財產局員工消費合作社印:η 10 第一反應槽 11 第一注入裝置 12 混合器 13 違送管線 14 第二反應槽 15 第二注入裝置 16 混合器 17 運送管線 18 第三反應槽 19 混合器 2〇 過濾系統 2 2 微過濾槽 2 4 淤泥保時槽 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -9 - 548243 A7 _______ B7 五、發明説明（7 ) 2 6 逆洗槽 2 8 微過濾膜 (請先閱讀背面之注意事項再填寫本頁) 3 0 壓濾機- 較佳實施例之詳細描述： 本發明者發現一種新系統及方法，其應用某些鹽類在 選擇的p Η値範圍，由水溶液諸如飮用水或廢水中同時移 除砷及氟化物。如使用在本發明名詞、、同時移除砷及氟化 物〃意指砷及氟化物係以同樣處理方法移除，而不需分別 處理。 通常，本發明提供一種由水溶液中移除砷及氟化物之 系統及方法，包括+ 5價氧化狀態之砷（亦可能出現+ 3 價氧化狀態）及氟化物離子（游離氟化物陰離子），其特 徵爲水溶液係在ρ Η値爲5〜8之範圍，用鈣鹽及鐵鹽或 鋁鹽之組合物處理，形成帶有砷及氟化物之固體。然從水 溶液中過濾此等固體後，因而移除砷及氟化物固體。 經濟部智慧財產局員工消費合作社印髮 更明確地說，由水溶液中移除砷及氟化物包括砷酸鹽 離子形態的砷（+ 5價氧化狀態之砷）及氟化物離子。在 一實施例中，砷主要係以預-氧化作用步驟處理提供的 -+ 5價氧化狀態之砷。在標準狀況下，+ 3價及+ 5價氧 化狀態之砷通常發現其如A s 0 3 — 3 (亞砷酸鹽）及 As〇^3 (砷酸鹽）離子存在。爲更有效的移除砷時使用凝聚 作用處理，較佳者爲砷主要是以+ 5價氧化狀態出現。 提供+ 5價氧化狀態的砷，水溶液較佳者爲以預-氧 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -10- 548243 Α7 Β7 五、發明説明（8 ) 化作用步驟處理。任何適用的氧化作用處理均可以使用在 預-氧化作用步驟處理。適用的氧化作用處理包括，但不 限定於：臭氧處理、曝露於紫外線、漂白、氧化性化學藥 品或試劑諸如高錳酸鉀及相當物。選擇性地，預一氧化作 用步驟可以使用描述於下申請案中之方法執行：與本案同 時未審定之美國專利申請案序號09/894,228 (代理人案號 A-68635/AJT/MSS)及暫時性專利申請案序號60/2 1 6,759 (2000年7月7日申請，代理人案號P-68635/AJT/MSS)， 其揭示之整體結合在此以供參考。明確地說，如進一步描 在其中，水溶液係在pH値爲3〜5之範圍，用過氧化氫 及鐵鹽或亞鐵鹽之組合物處理之。在選擇的p Η値範圍內 過氧化物及鐵鹽之組合物，可促進砷由+ 3價狀態氧化作 用成+ 5價狀態之砷。而喜愛此預-氧化作用步驟之際， 應該瞭解此等一般技術，爲本發明不用預-氧化作用步驟 即可以實施。 下列預-氧化作用步驟或選擇性地其不使用預-氧化 作用步驟，水溶液係調節到Ρ Η値爲5〜8之範圍，加入 鈣鹽於水溶液中以促進氟化物離子之沈澱，形成帶有氟化 物之粒子。其次，將鐵或鋁爲底質的鹽類加入水溶液中。 鐵或鋁爲底質的鹽類形成金屬氫氧化物絮凝物或懸浮物， 其可吸收帶有砷酸鹽離子及氟化物粒子兩者，而形成帶有 不溶性砷及氟化物之固體。當處理時水溶液Ρ Η値係視需 要使用習知方法調節並維持在Ρ Η値爲5〜8之範圍。然 後較佳者爲以描述於下面細節之過濾法，由水溶液中移除 本紙張尺度適用中國國家標準（CNS〉A4規格（210X 297公釐） (請先閱讀背面之注意事項真填寫本 装· tr 經濟部智慧財4局員工消贫合作社r:J-製 -11 - 548243 Α7 Β7 五、發明説明（9) 帶有砷及氟化物之固體。水溶液之P Η値高於8時砷的移 除效力是大爲降低。 (請先閲讀背面之注意事項再填寫本頁) 在較佳實施例中，加上一添加步驟爲將凝聚劑及/或 絮凝劑加入水溶液中幫助帶有砷及氟化物之固體沈澱。本 發明任何適用的凝聚劑及/或絮凝劑均可使用。較佳者凝 聚劑及/或絮凝劑將是中等分子量有機聚合物，諸如具有 分子量範圍在2，500〜500，000者。 水溶液中氟化物初始濃度變化很大而典型地爲1〜 5，0 0 0 p p m範圍。水溶液中砷之初始濃度亦變化很 大而典型地爲0.010〜500ppm範圍。根據本發 明之方法，水溶液係調節到p Η値爲5〜8之範圍，最佳 者ρ Η値爲7 · 5。加入鈣鹽於水溶液中。較佳者鈣鹽爲 選自於氯化鈣、氫氧化鈣及碳酸鈣，最佳者爲氯化鈣。鈣 鹽可以是溶液形態加入水溶液中，其濃度則以鈣與氟化物 之莫耳比=1〜2莫耳之鈣與2莫耳之氟化物的比。如此 ，鈣加入水溶液中之真正數量，將依水溶液中氟化物濃度 而變化。 經濟部智慧財產局員工消費合作社印製 添加鈣鹽於水溶液中在列舉的ρ Η値範圍，促進氟化 物之沈澱，形成不溶性的螢石或二氟化鈣粒子。最佳者此 反應允許在一充足的時間內產生氟化物之沈澱。時間將依 水溶液中出現氟化物初始濃度及水溶液之流量而變化，而 通常爲在5分鐘到1小時範圍，最佳者以至少1 〇分鐘時 間。較佳者實質上所有氟化物都自水溶液中沈澱而出；無 論如何，描述於下之添加的凝聚劑及/或絮凝劑能夠加入 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） -12- 548243 Μ Β7548243 A7 B7 V. Description of the invention (3) There are sources of waste water such as fluoride and arsenic. In particular, devices made from gallium arsenide, which are commonly used in the telecommunications industry, are an important source of soluble arsenic in wastewater. Ion implantation of arsenic atoms in semiconductor substrates is another source. Fluoride-containing chemicals are commonly used in etching substrates, cleaning materials, and associated processing equipment, both of which introduce fluoride into wastewater. Arsenic atoms exist in four valence states (also known as oxidation states); that is, -3, 0, + 3, and + 5 valences. Under standard conditions, the valence states of + 3 and + 5 are found as, for example, As s03—3 (arsenite) and As s04—1 (arsenate) ions. In order to effectively remove arsenic by coacervation, arsenic should be in a +5 oxidized state, preferably the arsenate form. Arsenite is partially removed by techniques such as absorption and coagulation, but the mechanism is less effective because its main form, arsenite (酸 3 A s〇3) is a weak acid (p K a 1 9 _ 2 3), which is most effectively removed by absorption remaining in its P Η 値 unionized; that is, in the range of 5-8. In contrast, O-arsenic acid (Η 3 A s04, arsenic is in the +5 valence oxidation state) is a strong acid (p K a 1 about 2 · 2 0), which is an ionic form starting from P Η 値 about 2. Negatively charged forms are most effective for absorption and aggregation. Many conventional techniques have been used to remove arsenic from wastewater. For example, co-precipitation, alumina adsorption, and classical ion exchange with anionic resins have been used. This technology has achieved limited success and limited its removal efficiency to only about 95%. Newer technologies have been developed, such as US Patent No. 5,3 68,703, which disclose the use of electrochemical cells that electrochemically generate ferrous ions. A mild oxidizing condition is established with the addition of peroxide, which can oxidize ferrous ions to iron ions, thereby forming iron hydroxide. However, this paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297). &Quot;-(Please read the precautions on the back before filling out this page) • Packing. Order the Intellectual Property Bureau Staff Consumer Cooperatives * S衾 -6- 548243 A7 B7_ V. Description of the invention (4) (Please read the precautions on the back before filling out this page) After removing arsenic using ferric hydroxide. Another known technique is described in US Patent No. 5,908,557, in which trivalent arsenic is oxidized to pentavalent arsenic and then removed with an adsorption medium containing N-alkylpyridine. This newer technology can provide improvements in removal efficiency, but these technologies are cumbersome, require special equipment and / or specialty chemicals, and are not easy to install or operate, especially for private well water treatment. Fluoride removal techniques include the use of calcium and other compounds to precipitate fluoride in a single or multiple stage processing procedure, such as described in US Patent Nos. 4,145,282, 5,04 3,07 2 and .5,403,495. The removal efficiency of these technologies has changed somewhat, and it cannot deal with the removal of fluoride and the removal of arsenic. Therefore, it would be highly desirable to provide a system and method that can remove arsenic and fluoride to safety standards from aqueous solutions, especially tritium water or industrial waste water. In order to respond to various industrial water needs, public water use in metropolitan areas, private well water, etc., and water use in both developed and underdeveloped countries, it is expected that the system and method will be accommodative and fully robust. Consumption cooperation by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, “Printing” Description of the invention: Therefore, the object of the present invention is to provide an improved system and method for simultaneously removing arsenic and fluoride from an aqueous solution, especially tritium water or wastewater. More specifically, the present inventors have discovered a new system and method for pretreating and maintaining an aqueous solution in a certain pΗ 値 range using certain salts, and simultaneously removing arsenic and fluoride from the aqueous solution. Generally, the paper size of the present invention for removing arsenic and fluoride simultaneously from the aqueous solution is applicable to the Chinese National Standard (CNS) Α4 specification (210X297 mm) -7- 548243 Α7 Β7 Ministry of Economic Affairs, Intellectual Property Bureau, 1 Industrial Bureau, industrial and consumer cooperation. 11 ^ ¾ 5. Description of the invention (5) System and method, including arsenic in +5 valence oxidation state (+3 valence oxidation state may also occur) and fluoride (free fluoride anion), which is characterized in that the aqueous solution is at p Η Rhenium is in the range of 5 to 8 and is treated with a combination of a calcium salt and an iron salt or an aluminum salt to form a precipitate or solid with arsenic and fluoride. However, after filtering these solids from the aqueous solution, arsenic and fluoride were removed. In another aspect, the present invention provides a system and method for simultaneously removing arsenic and fluoride from an aqueous solution, including the following steps: providing an aqueous solution including arsenic and fluoride in the form of an arsenate ion. The pH of the aqueous solution is adjusted to a range of 5 to 8. When the pH of the aqueous solution is higher than 8, the effectiveness of removing arsenic is greatly reduced. Calcium salts are added to the aqueous solution to promote the precipitation of fluoride to form particles or floes with fluoride. Iron or aluminum-based salts are then added to the aqueous solution. Iron or aluminum-based salts form metal hydroxide floes or suspensions, which absorb particles with arsenate ions and fluoride to form a solid with arsenic and fluoride. Arsenic and fluoride-containing solids are then removed from the aqueous solution. In another aspect of the present invention, a system is provided that includes a first reaction tank for receiving and receiving an aqueous solution including arsenic and fluoride. The pH of the aqueous solution is adjusted to a range of 5 to 8, and the first injection device is coupled to the first reaction tank to inject the calcium salt into the aqueous solution. The first mixer is preferably coupled to the first reaction tank for the mixing of the aqueous solution to promote the precipitation of fluorides to form particles t with fluorides. The table-one reaction tank provides an aqueous solution to be received from the first reaction tank, wherein the pH of the aqueous solution can be adjusted and maintained in the range of 5 to 8 as needed. A second injection device is coupled to the second reaction tank, and iron or aluminum-based salts are injected into the aqueous solution. The better is that the second mixer is coupled to the water supply of the second reaction tank (read the precautions on the back before filling in this page). Binding and ordering-*-^ This paper size applies to China National Standard (CNS) A4 specifications ( 210X29 * 7 Gongchu) -8- 548243 Α7 Β7 V. Description of the invention (6) (Please read the precautions on the back before filling this page) Solution and salt are mixed to form metal hydroxide floc or suspension, which Absorb particles with arsenic ions and fluoride to form a solid with arsenic and fluoride. A filtration system is provided to remove solids, and includes one or more filter vessels having one or more filter membranes configured in a tubular sock configuration, and adapted to fit into a narrow channel and one or more sedimentation tanks. Brief description of the drawings: After reading the detailed description of the present invention, other objects and advantages of the present invention will become apparent. The reference graphic supplementary application is provided as follows, where: Figure 1: Graphs showing arsenate and arsenite absorption rates as a function of ρ Η 値. Fig. 2 is a block diagram of a processing system according to an embodiment of the system and method of the present invention. Figure 3: A graph showing the fluoride concentration according to the present invention. Figure 4: A graph illustrating arsenic concentration according to the present invention. Comparison table of main components Consumers Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs: η 10 First reaction tank 11 First injection device 12 Mixer 13 Illegal line 14 Second reaction tank 15 Second injection device 16 Mixer 17 Transport line 18 Three reaction tanks 19 Mixer 20 Filter system 2 2 Microfiltration tank 2 4 Sludge time tank The paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -9-548243 A7 _______ B7 V. Description of the invention ( 7) 2 6 Backwash tank 2 8 Microfiltration membrane (please read the precautions on the back before filling this page) 3 0 Filter press-Detailed description of the preferred embodiment: The inventor has discovered a new system and method, Using certain salts in the selected p Η 値 range, arsenic and fluoride are simultaneously removed from aqueous solutions such as rhenium water or wastewater. If used in the term of the present invention, the simultaneous removal of arsenic and fluoride means that arsenic and fluoride are removed in the same manner without separate treatment. Generally, the present invention provides a system and method for removing arsenic and fluoride from an aqueous solution, which includes arsenic in a valence of 5 valence (also possible with a valence of 3 valence) and fluoride ion (free fluoride anion), which The characteristic is that the aqueous solution is in the range of ρ Η 値 5 to 8 and is treated with a combination of calcium salt and iron salt or aluminum salt to form a solid with arsenic and fluoride. However, after filtering these solids from the aqueous solution, arsenic and fluoride solids were removed. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs More specifically, the removal of arsenic and fluoride from aqueous solutions includes arsenic in the form of arsenate ions (+ arsenic in the valence of 5 valence) and fluoride ions. In one embodiment, the arsenic is mainly arsenic in the-+ 5-valent oxidation state provided by the pre-oxidation step. Under standard conditions, arsenic in +3 and +5 valence states is usually found in the presence of ions such as As 0 3-3 (arsenite) and As〇 ^ 3 (arsenate). In order to use coagulation for more effective arsenic removal, it is preferable that arsenic mainly appears in the +5 oxidation state. Provide +5 oxidized arsenic. The preferred solution is the pre-oxygen paper standard applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) -10- 548243 Α7 B7 5. Description of the invention (8) Chemical action steps. Any suitable oxidation treatment can be used in the pre-oxidation step. Suitable oxidation treatments include, but are not limited to: ozone treatment, exposure to ultraviolet light, bleaching, oxidizing chemicals or reagents such as potassium permanganate and equivalents. Alternatively, the pre-oxidation step can be performed using the method described in the following application: U.S. Patent Application Serial No. 09 / 894,228 (Agent No. A-68635 / AJT / MSS) and interim No. 60/2 1 6,759 (applied on July 7, 2000, agent case number P-68635 / AJT / MSS), the entire disclosure of which is incorporated herein by reference. Specifically, as described further, the aqueous solution is treated with a combination of hydrogen peroxide and an iron salt or a ferrous salt at a pH range of 3 to 5. The combination of peroxide and iron salt in the selected range of pΗ 値 can promote the oxidation of arsenic from +3 valence to +5 arsenic. While loving this pre-oxidation step, it should be understood that these general techniques can be implemented in the present invention without the pre-oxidation step. The following pre-oxidation step or optionally it does not use the pre-oxidation step, the aqueous solution is adjusted to the range of P Η 値 5 ~ 8, calcium salts are added to the aqueous solution to promote the precipitation of fluoride ions, forming a band with Particles of fluoride. Second, iron or aluminum-based salts are added to the aqueous solution. Iron or aluminum-based salts form metal hydroxide floes or suspensions, which can absorb both arsenate ions and fluoride particles to form a solid with insoluble arsenic and fluoride. When processing, the aqueous solution P Η 値 is adjusted and maintained in a range of P Η 値 5 to 8 using conventional methods as needed. Then it is better to use the filtration method described in the following details to remove the paper from the aqueous solution. The paper size applies the Chinese national standard (CNS> A4 specification (210X 297 mm)) (Please read the precautions on the back first to fill in this package. tr Employees' Anti-Poverty Cooperative of the 4th Bureau of Wisdom and Finance of the Ministry of Economic Affairs r: J-made-11-548243 Α7 Β7 V. Description of the Invention (9) Solids with arsenic and fluoride. The removal efficiency is greatly reduced. (Please read the notes on the back before filling this page) In the preferred embodiment, an addition step is added to add coagulant and / or flocculant to the aqueous solution to help carry arsenic and fluorine. Solid precipitation of compounds. Any suitable coagulant and / or flocculant of the present invention can be used. Preferably, the coagulant and / or flocculant will be a medium molecular weight organic polymer, such as having a molecular weight in the range of 2,500 ~ 500, 000. The initial concentration of fluoride in the aqueous solution varies widely and is typically in the range of 1 to 5, 000 ppm. The initial concentration of arsenic in aqueous solution also varies widely and is typically in the range of 0.010 to 500 ppm. The method according to the invention ,water The solution is adjusted so that p p is in the range of 5 to 8. The best ρ Η 値 is 7 · 5. The calcium salt is added to the aqueous solution. The preferred calcium salt is selected from calcium chloride, calcium hydroxide and carbonic acid. Calcium, the best is calcium chloride. The calcium salt can be added to the aqueous solution in the form of a solution, and its concentration is based on the molar ratio of calcium to fluoride = 1 to 2 molar to the ratio of calcium to 2 molar. In this way, the true amount of calcium added to the aqueous solution will vary depending on the concentration of fluoride in the aqueous solution. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the addition of calcium salts to the aqueous solution in the enumerated range of ρ 促进 to promote the precipitation of fluoride, The formation of insoluble fluorite or calcium difluoride particles. The best reaction allows the precipitation of fluoride in a sufficient time. The time will vary depending on the initial concentration of fluoride in the aqueous solution and the flow rate of the aqueous solution, and is usually In the range of 5 minutes to 1 hour, the best is at least 10 minutes. Preferably, substantially all fluorides are precipitated from the aqueous solution; however, the coagulants and / or flocculants described below are added Can add This paper scale applicable Chinese National Standard (CNS) Α4 Specification (210X 297 mm) -12- 548243 Μ Β7
五、發明説明（1P 幫助氟化物及砷粒子兩者更完全的沈澱。 (請先閱讀背面之注意事項再填寫本頁) 其次，將鐡或鋁爲底質的鹽類加入水溶液中移除砷離 子。氟化鈣粒子係被以氫氧化物形態之鋁或鐵爲底質的凝 聚劑捲入及吸收，其亦合用於砷吸收及表面吸附之受質。 水溶液的p Η値係以習知的方法監測及視需要調節，並維 持在pH値爲5〜8之範圍，最佳者pH値爲7 . 5。任 何鐵或鋁爲底質的鹽類其在列舉的P Η値範圍，形成金屬 氫氧化物絮凝物或懸浮物均可使用，諸如氯化物或硫酸鹽 。例如，鐵鹽適用於本發明者可以選自氯化鐵、硝酸鐵、 硫酸鐵銨、氯化鐵銨、氫氧化鐵及氧化鐵等族群。鐵鹽因 它們形成金屬氫氧化物絮凝物吸收砷之ρ Η値範圍，較鋁 鹽之ρ Η値範圍寬廣而被喜愛使用。最佳者爲使用氯化鐵 〇 經濟部智慧財產局員工消費合作杜印製 圖1顯示Ρ Η値作爲函數之砷（砷酸鹽）吸收百分率 的吸收曲線。從圖1可見，本發明方法之目標，以調節水 溶液之Ρ Η値到5〜8之範圍、最佳者ρ Η値爲7 . 5促 進砷酸鹽之有效移除。此外，Ρ Η値高於8時移除砷的效 力是大爲降低。Ρ Η値在8以上時，能發生電荷倒轉，導 致砷從金屬氫氧化物絮凝物釋出。 鐵或鋁鹽類可以是溶液形態。將鐵或鋁爲底質的鹽類 加入水溶液中。如上所述，鐵或鋁鹽類其在列舉的ρ Η値 範圍，添加入水溶液中，促進金屬氫氧化物絮凝物或懸浮 物之形成，其吸收形成於先前步驟之主要爲砷酸鹽離子形 態的砷及鈣粒子（螢石或二氟化鈣）兩者。較佳者，此反 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -13- 548243 A7 B7 五、發明説明（士 (請先閲讀背面之注意事項再填寫本頁} 應允許在一充足的時間內發生給與砷酸鹽離子及鈣粒子吸 收。時間將依水溶液中出現氟化物及砷之初始濃度與水溶 液之流量而變化，而通常爲在5分鐘到1小時範圍，最佳 者以至少1 0分鐘時間。較佳者實質上所有砷酸鹽離子及 氟化物粒子都被金屬氫氧化物絮凝物所吸收，因而形成帶 有砷及氟化物之固體；無論如何，可加入添加凝聚劑及/ 或絮凝劑。 在較佳實施例，添加凝聚劑及/或絮凝劑係加入水溶 液中以幫助在過濾前更完全的沈澱。凝聚劑及/或絮凝劑 爲低至中等分子量的有機聚合物，而較佳者分子量範圍爲 2 ， 5〇◦〜5〇〇，〇〇Og/mo 1 e 。適用的凝聚 劑及/或絮凝劑之實施例，包括但不限制於E P I D Μ A ，DADMA C及聚丙烯醯胺之共聚物與DADMAC。 凝聚劑及/或絮凝劑係加入到足以幫助沈澱的量，通常出 現在水溶液中之濃度爲3〜3 0 0 p pm。 經濟部智慧財產局員工消費合作社印製 一旦形成帶有砷及氟化物之固體，它們即經由如描述 在下之過濾技術從水溶液中移除。本發明之方法是實質上 能夠移除所有水溶液中之砷及氟化物，尤其是本發明之處 理後砷的最終濃度通常爲等於或低於5 p p b，較佳者爲 等於或低於2 p P b，氟化物之濃度通常爲等於或低於 1〇p pm，較佳者爲等於或低於2 p pm。 本發明之方法可以使用任何適用的水處理系統實施， 並不限於以任何特別的設備或系統，無論如何，本方法較 佳者係實施於本發明之系統描述如下。本發明之系統的一 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -14- 548243 Α7 Β7 五、發明説明（1全 實施例說明如圖2。圖2顯示砷及氟化物之一移除系統， 通常包含一個或更多反應槽，伴隨混合器及過濃系統。較 佳者，過濾系統係描述於 u . S · Patent Nos .5，871，648 及 5，904 ’ 853型式者，其揭示之整體結合在此以供 參考。明確地說，水溶液中含有之砷及氟化物係餵進第一 反應槽（1 0 )。第一反應槽水溶液之p Η値使用習知的 調節裝置調節到5〜8之範圍，而氯化物鹽諸如氯化鈣經 由弟一注入裝置（11)加入第一反應槽（10)。第一 注入裝置（1 1 )爲任何適用的化學運送單元。加入鈣鹽 直到其濃度到達鈣與氟化物之莫耳比二1〜2莫耳之鈣與 2莫耳之氟化物的比。較佳者，第一注入裝置（1 1 )， 如氟化物離子比電極（I S Ε )其包括製程控制特色而提 供在第一反應槽（1 0 )中氟化物濃度之真實時間監測。 溶液以混合器（1 2 )攪拌促進其成份之混合。溶液 以混合器（1 2 )混合一段時間允許其氟化物粒子實質上 完全沈澱。反應時間將依第一反應槽（1 〇 )尺寸及水溶 液中初始氟化物濃度而變化，最佳者至少1 〇分鐘時間。 然後將溶液經由運送管線（1 3 )餵進第二反應槽（ 1 4 )。水溶液之ρ Η値經監測及視需要而使用習知的調 節裝置調節並維持在5〜8之範圍。經由第二注入裝置（ 1 5 )加入鐵或鋁鹽類諸如硫酸鐵或氯化鐵於第二反應槽 (14)，溶液以混合器（1 6 )攪拌確保其成份之混合 。選擇性地，鐵或鋁鹽類可以經由安置於運送管線（1 3 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） L------------- (請先閲讀背面之注意事項再填寫本頁) 、1Τ 經濟部智慧財產局員工消費合作社印製 -15- 548243 A7 B7 五、發明説明（1会 (請先閲讀背面之注意事項再填寫本頁) )直列的混合器加入溶液中。此鹽類可以是固體或較佳者 爲液體形態。水溶液中鐵或鋁鹽類濃度，將強度依出現在 水溶液中砷及氟化物含量而定，較佳者爲普通在1 0〜 1 0 0 0 P P m 〇 溶液以混合器（1 6 )混合一段時間，允許其溶液與 金屬氫氧化物絮凝物有充分接觸時間。此時間典型地至少 1 0分鐘。 一旦形成金屬氫氧化物，將溶液經由運送管線（1 7 )餵進第三反應槽（1 8 )。水溶液之p Η値假如需要再 調節並維持在5〜8之範圍。溶液以混合器（1 9 )攪拌 促進良好的成份之混合。在此ρ Η値範圍，不溶性之砷離 子及15粒子都被吸收在金屬氫氧化物絮凝物上，形成不溶 性帶有砷及氟化物之固體。此反應係允許其發生一段時間 。較佳者，第三反應槽（1 8 )尺寸之水溶液反應留滯時 間爲5分纟里或更久’最佳者至少1 〇分鐘。較佳實施例中 ，爲幫助形成帶有砷及氟化物之固體，可將凝聚劑及/或 絮凝劑加入進料槽（18)。 經濟部智慧財產局員工消費合作社印製 帶有砷及氟化物之固體一旦形成，以幫浦或重力餵進 過濾系統（2 0 )。任何適用的過濾系統均可使用。圖2 說明較佳實施例之過瀘系統。圖2之過瀘系統（2 0 )普 通包含薄膜過濾系統諸如微過濾系統，更詳細地描述於 U . S . Patent Nos .5，871，648 及 5，904，853 ’其揭示之整體結合在此以供參考。 在此實施例，過濾系統通常包括一個或更多過濾器或微過 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16- 548243 經濟部智慧財產局員工消費合作社印製 A7 _ B7五、發明説明（id 濾槽（2 2 )及沈降或淤泥保持槽（2 4 )。逆洗槽（ 2 6 )較佳者可以安置於過濾槽（2 2 )之前使用。過濾 槽（2 2 )以兩種模式操作；即爲過濾槽操作模式及過濾 槽逆洗模式。過濾槽（2 2 )通常包括管狀 > 襪套〃組態 之微過濾膜。膜襪套係置放在細溝管上防止使用時襪套之 崩潰。膜材料是可從商場上各種來源取得，較佳者其細孔 尺寸在0 . 5〜1 0 範圍，最佳者細孔尺寸爲1 /zm 〇 當操作模式時，帶有砷及氟化物之固體係從水溶液中 脫水及過瀘。水溶液從過瀘容器經薄膜而抽取，當水溶液 通過薄膜時粒子並不通過，代之於膜表面外面建起。、、淸 潔"水溶液自過濾槽頂部溢流出排放或循環。淸潔水溶液 實質上沒有砷及含有砷濃度等於或小於1 〇 p p b，更佳 者砷濃度等於或小於2 p P b ;實質上沒有氟化物及含有 氟化物濃度等於或小於1 〇 p p m，更佳者氟化物濃度等 於或小於2 p p m。 更明確地說，過瀘槽（2 2 )較佳者設有微過瀘膜（ 2 8 )陣列。較佳者，微過濾膜係包含管狀 > 襪套〃組態 成最大表面積。膜襪套係置放在細溝管上防止使用時襪套 之崩潰。爲達成高流量及通量値，爲數甚多之膜或膜組件 各含有甚多的單獨過濾襪套可以使用。微過濾膜較佳者其 細孔尺寸在〇 . 5〜1 0 // m範圍，最佳者細孔尺寸爲 0 · 5〜1 . O/zm。據發現通過〇 . 5〜1 , 〇#m微 過濾膜之處理廢水通量能在200〜1 500GFD ( 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) -17- 548243 A7 B7 五、發明説明（1会 (請先閲讀背面之注意事項再填寫本頁) ga 1/f t2/day)，理想的通量爲 800 GFD 。此外，本系統流量爲在1 0〜1 0 0 0 0 g a 1 / min·。 微過濾膜較佳者以卡匣式或組件式或以含有膜陣列之 預成形層板提供。在各案，膜均方便於組裝或自頂部旋出 項圈配件移除。選擇性地，整個卡匣或層板可在使用中移 除。微過濾膜提供高回收靜頭過濾陣列之確實的粒子分離 。此靜頭過瀘在低壓（3〜2 5 p s i ，較佳者爲5〜 經濟部智慧財產局員工消費合作社印製 1 0 p s i )及高流量下有效地操作，允許一次通過供應 水9 9 . 9 %排放之處理，且其中橫過微過濾膜之壓力差 不超過2 5 p s i 。當過濾時集積在膜表面之固體係定期 地從膜表面逆洗出，以確保連續地淸潔過濾介質。目前， 本發明使用較佳之過濾襪套，包含鐵氟龍塗層在聚丙烯或 聚乙烯檀狀襯底物。該過瀘襪套可自W . L . Gore取得。其 他較佳之過濾襪套爲 National Fiter Media ，Salt Lake City，Utah所製造，係由聚丙烯組成編織膜結合在聚丙烯或 聚乙烯檀狀襯底物。因爲膜是簡單又便宜，一些操作認爲 它更省成本而以從膜淸除污染物取代膜襪套。無論如何， 應該注意的爲膜是非常的耐自酸、鹼、還原劑及一些氧化 劑之化學侵鈾。膜的除垢是以酸洗達成，而在去除生物垢 時可以過氧化氫、稀漂白水或其他適當試劑處理完成。 從膜表面及過濾容器移除帶有砷及氟化物之固體，過 濾槽（2 2 )係安置於逆洗模式。微過濾膜（2 8 )係定 期地逆洗保持高流量通過系統。較佳者係以定期逆洗微過 本紙張尺度適用中國國家標準（iNS ) A4規格（210X297公釐） ~ -18 - 548243 A7 B7 ____ 五、發明説明（ιέ (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 濾膜從膜表面移除固體，且排放到微過濾膜（2 8 )所在 之過®槽（2 2 )。較佳者逆洗是當微過爐膜（2 8 )之 壓力約達6 p s i時開始。定期的、短時間逆洗可移除任 何從微過濾膜襪套壁築起之污染物。逆洗是達成了但並不 限於重力體系，即一其閥是開著而過濾陣列上面水裝塡空 隙1〜2呎提供脫落過濾餅之力。過濾槽（2 2 )內驅出 之固體材料，然可轉移到淤泥保持槽（2 4 )供進一步固 體處理。如描述之微過濾是全自動化，且可2 4小時一天 、一星期七天之運作，使自操作者投入最少。本系統可以 使用程序邏輯控制（P L C )全自動化，其能與監督者及 控制資料取得系統（S C A D A )溝通。簡單及堅固的硬 體連續地監測流動液及流出液之特性且需要時可調節化學 進料。自動化監測參數之例包括P Η値、濁度、氧化還原 電位、粒子Ζ電位及金屬污染物濃度。製程拓展及細調以 連續監測製程參數接著以既知技術控制調整達成。在逆洗 模式，流動系統係反過來其過濾陣列上面裝塡空隙水是反 流。這是以開啓在過濾槽（2 2 )之閥達成。粒子及淤泥 沈降在過濾槽（2 2 )底部，然以幫浦或重力餵進固體淤 泥保持槽（2 4 )及移除。假如期望的話，壓濾機（3 0 )可使用在提供粒子進一步脫水。値得注意的爲在描述處 理系統之一型時，本發明之方法可實施在廣泛不同型之各 種處理系統，諸如重力沈降及橫一流過濾系統。 下列具希望的實施例僅提供作說明目的，而無意以任 何方法限制本發明： I紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） ' -19- 548243 Α7 Β7 五、發明説明（1> 實施例1 : (請先閲讀背面之注意事項再填寫本頁) 一砷化鎵太陽電池製造設施產出由砷及酸性氟化物組 成的混合廢水溶液溪流。砷的來源爲從氟化氫蝕刻處理及 胂化物氣體洗淨器。廢水中砷濃度在〇〜2 0 0 0 p D m 範圍。氟化物駑$在0〜5 Ο Ο ρ p m範圍。廢水的流量 爲在20〜50ga 1/mi η ·。根據本發明，在此廢 水處理系統砷係連續地移除至低於排放極限之5 0 p p b ，Ρ Η値在5〜8間以氫氧化鐵吸收。氟化物以沈澱法成 螢石而移除至小於1 〇 p p m，要求下如以氟化物離子比 電極感應器讀數量測。過濾系統之壓力，明確地說，橫過 膜過瀘器之壓力範圍在3〜1 Op s i ，平均爲5p s i 。平均通量估計爲8 0 0 G F D。高流量、低壓力過濾系 統較佳者係設計爲自動化操作及較佳者操作2 4小時一天 ，使自操作者投入最少。從世界任何地方經由數據機，現 場並能控制及故障解決。 經濟部智慧財產局員工消費合作社印製 在典型的實施例中，含有溶解性氟化物及砷兩者的廢 水導入預保留槽，廢水ρ Η値調到約8。然將廢水導入第 一反應槽（1 0 )中，注入氯化鈣溶液（試劑溶液3 5 % )直到其濃度到達且維持鈣與氟化物之莫耳比=1〜2莫 耳之鈣與2莫耳之氟化物的比之範圍。鈣劑量依實際監測 氟化物濃度而定，較佳者，在第一反應槽（1 〇 )中以氟 化物離子比電極（I S Ε )真實時間監測之。注入鈣溶液 能經由線上混合器或直接進入第一反應槽（1 〇 )中。第 一反應槽（1 0 )在約5 0 R Ρ Μ充分攪拌及ρ Η値維持 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -20- 548243 A7 _ B7 五、發明説明（ (請先閲讀背面之注意事項再填寫本頁) 在5〜8，較佳者爲在7。所得結果的螢石沈澱物及水溶 液然轉移到第二反應槽（1 4 )中，在此含有水性砷及氟 化鈣沈澱物之溶液使用3 5 %氯化鐵溶液處理，其較佳者 爲以連續注入。P Η値維持在5〜8範圍，注意p Η値不 能超過8，否則吸收在絮凝物粒子的砷，由於表面電荷反 轉而不會脫附。如此得到的氫氧化鐵絮凝物粒子含有砷及 氟化鈣沈澱物兩者。爲強化絮凝物之凝聚及可過瀘性，分 子量約2 5 0 0 0 0之ΕΡ I - DMA陽離子聚合物導入 第三反應槽（1 8 )。然後使此大而易於過濾之粒子，較 佳者在5 p s i壓力差經微過濾系統（2 〇 )過濾。 實施例2 : 經濟部智慧財產局員工消費合作社印製 兩個化學拋棄物同時發生在系統中，首先，含有 1 3 · 8 7砷溶液之5加侖罈投入本系統，接著含有 1 · 8 5 5公升氟化物溶液之1加侖罈投入本系統。首先 ’水稀釋效應以計算及量測兩者作比較處理效率。此數量 爲第一反應槽之10.8ppm砷及1441ppm氟化 物之最大理論濃度。3 0分鐘後，在過瀘槽（僅稀釋）未 處理之理論濃度爲286ppb砷及38 . 2ppm氟化 物；60分鐘後，爲25〇ppb砷及33 . 4ppm氟 化物；9 0分鐘後，爲1 〇 4 P P b砷及1 3 . 9 p p m 氟化物；120分鐘後，爲34·4ppb砷及4.6 p p m氟化物。 真正最大入口濃度在1 2分纟里後爲8 6 3 . 7 p pm 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐Ί~— " -21 - 548243 A7 B7 五、發明説明（1会 氟化物。3 0分鐘後第一次分析測試結果入口砷濃度爲 2 · 4 ρ p m。拋投1小時4 8分鐘後，真正最大系統出 口氟化物濃度爲6 · 0 6 p p m。測試1小時後’第二次 測試時真正最大砷濃度爲1 3 . 6 P P b。根據本發明之 實施例，圖3及4圖式說明各別以時間爲函數時，氟化物 及砷之濃度。 本系統使用化學處理連續運作4小時移除氟化物及砷 。當拋投之際，平均流入系統之流量爲1 5 . 2 2 g p m 。平均氯化鈣劑量爲5 2 . 7 9 m 1 /m i η ;平均鋁酸 鈉劑量爲9 . 5 8 m 1 /m i η ;平均氯化鐵劑量爲 1 · 4 lml/mi η。氯化鈣劑量濃度爲3 〇% ;氯化 鐵劑量濃度爲3 5 % ; Ε Ρ I — D Μ Α劑量濃度爲5 % ; 鋁酸鈉劑量濃度爲3 8 %。下面表1資料顯示根據本發明 之稀釋及化學處理兩者，可減低砷及氟化物含量至可接受 的程度。 (請先閲讀背面之注意事項再填寫本頁) 、11 -^1 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（210X29?公釐） -22- 548243 A7 B7 五、發明説明（20_ ---- 砷 氟化物 稀釋 處理及稀 稀釋 處理及稀 釋 釋 理論最大入口濃度 10.8 1441 - (ppm) 理論最大出口濃度 0.323 - 43.2 (ppm) 貫際最大入口濃度 - 2.4 - 863.7 (ppm) 實際最大出口濃度 - 0.0136 - 6.06 (ppm) 濃度減低 97.0% 99.4% 97.0% 99.3% 回收 0% 81.1% 0% 76.6% (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 誠如前面描述及實施例所授，使用本發明提供之相同 製程由水溶液中 移除砷及氟化物之一種改進的方法。前面描述之特定 具體化及本發明實施例呈獻說明及描述目的，雖然本發明 以某些進行中實施例說明，它是不會被解釋而限制。它們 並不有意於澈底的或限制本發明精密的形式揭示之，而依 照上授顯然的許多修改、具體化及變化是可能的。本發明 範疇有意包含在此揭示的一般性的範圍，及到此爲止之附 加申請與它們的相當者。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -23-V. Description of the invention (1P helps more complete precipitation of both fluoride and arsenic particles. (Please read the precautions on the back before filling this page) Second, add the salts of rhenium or aluminum as the substrate to the aqueous solution to remove arsenic Ions. Calcium fluoride particles are entangled and absorbed by agglomerates with aluminum or iron in the form of hydroxides, and they are also used as substrates for arsenic absorption and surface adsorption. The method monitors and adjusts as needed, and maintains the pH 値 in the range of 5 ~ 8, the best pH 値 is 7.5. Any iron or aluminum as the substrate salt in the listed P Η 値 range, the formation Either metal hydroxide floes or suspensions can be used, such as chlorides or sulfates. For example, iron salts are suitable for the present inventors and may be selected from the group consisting of iron chloride, iron nitrate, ammonium iron sulfate, ammonium iron chloride, hydroxide Iron and iron oxide and other groups. Iron salts are favored for use because they form metal hydroxide flocs that absorb arsenic in a range of ρ Η 値, which is wider than ρ Η 値 in aluminum salts. The best is to use iron chloride. Department of Intellectual Property Bureau, consumer cooperation, Du printed 1 Shows the absorption curve of P 砷 as a function of arsenic (arsenate) absorption percentage. As can be seen from FIG. 1, the objective of the method of the present invention is to adjust the P 水溶液 of the aqueous solution to a range of 5 to 8 and the best ρ Η 値Promote the effective removal of arsenate for 7.5. In addition, the effectiveness of arsenic removal is greatly reduced when P Η 値 is higher than 8. When P 以上 is higher than 8, the charge inversion can occur, resulting in arsenic from metal hydrogen. Oxide flocs are released. Iron or aluminum salts can be in the form of a solution. Salts with iron or aluminum as the substrate are added to the aqueous solution. As mentioned above, iron or aluminum salts are added in the enumerated range of ρ Η 値. Into an aqueous solution, it promotes the formation of metal hydroxide floes or suspensions, which absorb and form both arsenic and calcium particles (fluorite or calcium difluoride) mainly in the form of arsenate ions in the previous step. In addition, this paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -13- 548243 A7 B7 V. Description of the invention (Just (please read the notes on the back before filling this page) Arsenate ions and Calcium particle absorption. The time will vary depending on the initial concentration of fluoride and arsenic in the aqueous solution and the flow rate of the aqueous solution, but is usually in the range of 5 minutes to 1 hour, the best being at least 10 minutes. The better is essentially All arsenate ions and fluoride particles are absorbed by the metal hydroxide flocculant, thereby forming a solid with arsenic and fluoride; however, a flocculant and / or flocculant can be added. In a preferred embodiment Coagulant and / or flocculant are added to the aqueous solution to help more complete precipitation before filtration. Coagulant and / or flocculant are low to medium molecular weight organic polymers, and the preferred molecular weight range is 2, 5 〇◦ ～ 50,000。 g / mo 1 e. Examples of suitable coagulants and / or flocculants include, but are not limited to, EPID M A, DADMA C, and a copolymer of polyacrylamide and DADMAC. The coagulant and / or flocculant are added in an amount sufficient to aid precipitation, and usually appear in the aqueous solution at a concentration of 3 to 300 p pm. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Once solids with arsenic and fluoride are formed, they are removed from the aqueous solution by filtration techniques as described below. The method of the present invention is capable of removing arsenic and fluoride in substantially all aqueous solutions. In particular, the final concentration of arsenic after the treatment of the present invention is usually equal to or lower than 5 ppb, preferably equal to or lower than 2 p P b. The concentration of fluoride is usually equal to or lower than 10 p pm, preferably equal to or lower than 2 p pm. The method of the present invention can be implemented using any applicable water treatment system, and is not limited to any special equipment or system. In any case, the better method is implemented in the system of the present invention as described below. A paper size of the system of the present invention is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -14- 548243 A7 B7 V. Description of the invention (1 The full embodiment is illustrated in Figure 2. Figure 2 shows arsenic and fluorine One of the compound removal systems usually includes one or more reaction tanks with a mixer and an over-concentration system. Preferably, the filtration system is described in U.S. Patent Nos. 5,871,648 and 5,904 ' For the 853 type, the entirety of its disclosure is incorporated herein for reference. Specifically, the arsenic and fluoride contained in the aqueous solution are fed into the first reaction tank (1 0). The known adjusting device is adjusted to a range of 5 to 8, and a chloride salt such as calcium chloride is added to the first reaction tank (10) through the first injection device (11). The first injection device (1 1) is any applicable chemistry Conveying unit. Calcium salt is added until its concentration reaches the molar ratio of calcium to fluoride. 1 ~ 2 molar ratio of calcium to 2 molar ratio. Preferably, the first injection device (1 1), such as Fluoride ion ratio electrode (IS Ε) which includes process control features For real time monitoring of fluoride concentration in the first reaction tank (1 0). The solution is stirred with a mixer (1 2) to promote the mixing of its components. The solution is mixed with a mixer (1 2) for a period of time to allow its fluoride particles It is substantially completely precipitated. The reaction time will vary depending on the size of the first reaction tank (10) and the initial fluoride concentration in the aqueous solution, and the optimal time is at least 10 minutes. Then the solution is fed into the first via the transport line (1 3). Two reaction tanks (1 4). The ρ 水溶液 of the aqueous solution is adjusted and maintained in the range of 5 to 8 by monitoring and using a conventional adjusting device as needed. Iron or aluminum salts are added through the second injection device (1 5). Such as ferric sulfate or ferric chloride in the second reaction tank (14), the solution is stirred by a mixer (1 6) to ensure the mixing of its ingredients. Alternatively, iron or aluminum salts can be placed in the transport line (1 3 Paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) L ------------- (Please read the precautions on the back before filling this page), 1T Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives -15- 548243 A7 B7 Description of the invention (1 session (please read the precautions on the back before filling this page)) Add the inline mixer to the solution. This salt can be solid or better in liquid form. The concentration of iron or aluminum salts in the aqueous solution The strength depends on the arsenic and fluoride content in the aqueous solution, preferably the solution is generally mixed with a mixer (16) at a range of 10 to 100 PP 〇, allowing the solution and metal hydrogen Oxide flocs have a sufficient contact time. This time is typically at least 10 minutes. Once the metal hydroxide is formed, the solution is fed into the third reaction tank (1 8) via the transfer line (1 7). The p of the aqueous solution should be adjusted and maintained in the range of 5 to 8 if necessary. The solution is stirred with a mixer (19) to promote good mixing of the ingredients. In this ρ Η 値 range, insoluble arsenic ions and 15 particles are absorbed on the metal hydroxide flocculant to form an insoluble solid with arsenic and fluoride. This reaction is allowed to occur for a period of time. Preferably, an aqueous solution of the third reaction tank (18) has a reaction lag time of 5 minutes or more, and the best is at least 10 minutes. In a preferred embodiment, to help form a solid with arsenic and fluoride, a coagulant and / or flocculant can be added to the feed tank (18). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Once solids with arsenic and fluoride are formed, they are fed into the filtration system by pump or gravity (20). Any applicable filtration system can be used. FIG. 2 illustrates a transition system according to a preferred embodiment. The filter system (20) of FIG. 2 generally includes a membrane filtration system such as a microfiltration system, which is described in more detail in U.S. Patent Nos. 5,871,648 and 5,904,853. For reference. In this embodiment, the filtering system usually includes one or more filters or paper sizes that are slightly smaller than this paper. Applicable to China National Standard (CNS) A4 (210X297 mm) -16- 548243 Printed by A7, Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs _ B7 V. Description of the invention (id filter tank (2 2) and sinking or silt holding tank (2 4). The backwash tank (2 6) is better to be placed before the filter tank (2 2). Filter tank ( 2 2) Operate in two modes; namely, filter tank operation mode and filter tank backwashing mode. The filter tank (2 2) usually includes a micro-filtration membrane with a tube & sock configuration. The film sock is placed in a fine groove The tube prevents the sock from collapsing during use. The membrane material can be obtained from various sources in the shopping mall. The preferred one has a pore size in the range of 0.5 to 10, and the best one has a pore size of 1 / zm. At the time, the solid with arsenic and fluoride was dehydrated and tritium from the aqueous solution. The aqueous solution was extracted from the tritium container through the thin film. When the aqueous solution passed through the thin film, the particles did not pass through and it was built on the outside of the film surface. Jie Jie " Aqueous solution from the filter tank Partial overflow discharges or circulates. The clean water solution is substantially free of arsenic and contains arsenic concentration equal to or less than 10 ppb, more preferably the arsenic concentration is equal to or less than 2 p P b; virtually no fluoride and contains fluoride concentration equal to or Less than 10 ppm, more preferably, the fluoride concentration is equal to or less than 2 ppm. More specifically, it is preferable that the perforated tank (2 2) is provided with a micro perforated membrane (2 8) array. More preferably, microfiltration The membrane system includes a tube > sock cover configured to maximize surface area. The film sock cover is placed on a narrow groove tube to prevent the sock from collapsing during use. In order to achieve high flow and flux 値, there are many membranes or membrane modules. There are many separate filter socks that can be used. Microfiltration membranes with a fine pore size in the range of 0.5 ~ 1 0 // m, and the best with a fine pore size of 0 · 5 ~ 1. O / zm. According to It was found that the flux of treated wastewater through 0.5 ~ 1, 〇 # m microfiltration membrane can be 200 ~ 1 500GFD (this paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) (please read the note on the back first) Please fill in this page for matters) -17- 548243 A7 B7 V. Description of Invention (1 (Please read the notes on the back before filling in this page) ga 1 / f t2 / day), the ideal flux is 800 GFD. In addition, the system's flow rate is between 1 0 ~ 1 0 0 0 0 ga 1 / min · The microfiltration membrane is preferably provided as a cassette or a module or as a pre-formed laminate containing a membrane array. In each case, the membrane is easy to assemble or remove from the top by removing the collar accessories. Optionally, the entire The cassette or shelf can be removed during use. Microfiltration membranes provide reliable particle separation with high recovery static head filtration arrays. This static head is operated efficiently under low pressure (3 ~ 25 psi, preferably 5 ~ 10 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs) and high flow rate, allowing one pass of water supply 9 9. 9% emissions treatment, and the pressure difference across the microfiltration membrane does not exceed 25 psi. The solids accumulated on the membrane surface during filtration are periodically backwashed from the membrane surface to ensure continuous cleaning of the filter media. Currently, the present invention uses a preferred filter sock, which includes a Teflon coating on a polypropylene or polyethylene sandal substrate. The stockings are available from W. L. Gore. Other preferred filter socks are made by National Fiter Media, Salt Lake City, Utah. They are made of polypropylene and are combined with polypropylene or polyethylene sandal substrate. Because the membrane is simple and cheap, some operations consider it to be more cost-effective and replace the sock with a membrane that removes contaminants. In any case, it should be noted that the membrane is very resistant to chemical invasion of uranium by acids, alkalis, reducing agents and some oxidizing agents. Membrane descaling is achieved by pickling, and can be treated with hydrogen peroxide, dilute bleach or other appropriate reagents when removing bioscale. The arsenic and fluoride-containing solids were removed from the membrane surface and the filter container, and the filter tank (2 2) was placed in a backwash mode. The microfiltration membrane (2 8) is periodically backwashed to maintain high flow through the system. The better one is to periodically backwash the paper, and apply the Chinese National Standard (iNS) A4 specification (210X297 mm) ~ -18-548243 A7 B7 ____ V. Description of the invention (ιέ (Please read the precautions on the back before (Fill in this page) The printed membranes printed by the employees ’cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs remove solids from the membrane surface and discharge them to the ® tank (2 2) where the microfiltration membranes (2 8) are located. Micro-furnace membrane (2 8) pressure starts at about 6 psi. Periodic, short-term backwashing can remove any contaminants that build up from the wall of the microfiltration membrane socks. Backwashing is achieved but not limited to gravity The system, that is, the valve is open, and the water storage space above the filter array is 1 to 2 feet to provide the force to fall off the filter cake. The solid material driven out of the filter tank (2 2) can be transferred to the sludge holding tank (2 4) For further solids treatment. As described, the microfiltration is fully automated, and can be operated 24 hours a day, seven days a week to minimize operator input. This system can be fully automated using program logic control (PLC). Able to communicate with supervisors and control information SCADA communication. Simple and sturdy hardware continuously monitors the characteristics of flowing and effluent fluids and adjusts the chemical feed when needed. Examples of automated monitoring parameters include P 参数, turbidity, redox potential, particles Z potential and metal pollutant concentration. Process expansion and fine tuning to continuously monitor process parameters and then achieve control adjustments with known technology. In the backwash mode, the flow system is in turn installed on the filter array and the gap water is reversed. This is This is achieved by opening the valve in the filter tank (2 2). Particles and sludge settle at the bottom of the filter tank (2 2), then fed to the solid sludge holding tank (2 4) by pump or gravity and removed. If desired, The filter press (30) can be used to provide further dehydration of the particles. It should be noted that when describing one type of processing system, the method of the present invention can be implemented in a wide variety of processing systems, such as gravity settlement and horizontal flow. Filtration system. The following promising examples are provided for illustrative purposes only, and are not intended to limit the invention in any way: I Paper size applies to Chinese national standards (CN S) Α4 specification (210 × 297 mm) '-19- 548243 Α7 Β7 V. Description of the invention (1 > Example 1: (Please read the precautions on the back before filling this page) A gallium arsenide solar cell manufacturing facility output A mixed wastewater solution stream consisting of arsenic and acid fluoride. The source of arsenic is from hydrogen fluoride etching treatment and tritium gas scrubber. The concentration of arsenic in the wastewater ranges from 0 to 2000 p Dm. 0 ~ 5 Ο Ο ρ pm range. The flow rate of wastewater is 20 ~ 50ga 1 / mi η · According to the present invention, the arsenic system of the wastewater treatment system is continuously removed to 50 ppb below the discharge limit, P Η Rhenium is absorbed by iron hydroxide between 5 and 8. Fluoride is precipitated into fluorite and removed to less than 10 p p m. It is required to read the quantity by using a fluoride ion ratio electrode sensor. The pressure of the filtration system, specifically, the pressure across the membrane filter ranges from 3 to 1 Op s i, with an average of 5 p s i. The average flux is estimated at 800 G F D. The high-flow, low-pressure filtration system is better designed for automatic operation and better operation for 24 hours a day, so that the operator's investment is minimal. Via modems from anywhere in the world, and can control and troubleshoot on-site. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In a typical embodiment, waste water containing both dissolved fluoride and arsenic is introduced into a pre-reservation tank, and the waste water ρ Η 値 is adjusted to about 8. Then, the wastewater is introduced into the first reaction tank (10), and the calcium chloride solution (reagent solution 35%) is injected until the concentration reaches and maintains the molar ratio of calcium to fluoride = 1 to 2 molar calcium and 2 Range of mole ratios. The calcium dose depends on the actual monitoring of the fluoride concentration. Preferably, the calcium ion is monitored in the first reaction tank (10) with a fluoride ion specific electrode (I S Ε) in real time. The calcium solution can be injected via an in-line mixer or directly into the first reaction tank (10). The first reaction tank (1 0) was fully stirred at about 50 rpm and maintained at ρ Η 値 to maintain the size of this paper. Applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -20- 548243 A7 _ B7 V. Description of the invention ((Please read the precautions on the back before filling in this page) In 5 ~ 8, preferably in 7. The fluorite precipitate and aqueous solution obtained are then transferred to the second reaction tank (1 4), here The solution containing aqueous arsenic and calcium fluoride precipitates is treated with a 35% ferric chloride solution, which is preferably continuously injected. P Η 値 is maintained in the range of 5 ~ 8. Note that p Η 値 cannot exceed 8, otherwise it will be absorbed. The arsenic in the floc particles will not be desorbed due to the reversal of the surface charge. The ferric hydroxide floc particles thus obtained contain both arsenic and calcium fluoride precipitates. The EP I-DMA cationic polymer with a molecular weight of about 2 5 0 0 0 0 is introduced into the third reaction tank (1 8). Then the large and easily filtered particles are preferably passed through a microfiltration system at a pressure difference of 5 psi (2 〇) Filtration Example 2: Employees' cooperation in intellectual property bureau of the Ministry of Economic Affairs The company printed two chemical discards at the same time in the system. First, a 5 gallon jar containing 1 3 · 8 7 arsenic solution was put into the system, and then a 1 gallon jar containing 1. 8 5 5 liters of fluoride solution was put into the system. First of all, the effect of water dilution is used to calculate and measure the two to compare the treatment efficiency. This amount is the maximum theoretical concentration of 10.8 ppm arsenic and 1441 ppm fluoride in the first reaction tank. After 30 minutes, the solution was passed through the tank (only diluted) ) Untreated theoretical concentration is 286 ppb arsenic and 38.2 ppm fluoride; after 60 minutes, it is 25 ppb arsenic and 33.4 ppm fluoride; after 90 minutes, it is 104 ppb arsenic and 13.9 ppm Fluoride; After 120 minutes, it is 34 · 4ppb arsenic and 4.6 ppm fluoride. The true maximum inlet concentration is 8 6 3. 7 p pm after 12 minutes. This paper size applies the Chinese National Standard (CNS) A4 specification ( 210X 297 mm Ί ~ — " -21-548243 A7 B7 V. Description of the invention (1 will be fluoride. The first analysis test results after 30 minutes The inlet arsenic concentration is 2 · 4 ρ pm. Throw 1 hour 4 After 8 minutes, the true maximum system outlet fluoride concentration was 6.06 ppm. After 1 hour of testing, the true maximum arsenic concentration in the second test is 13.6 PP b. According to the embodiment of the present invention, FIGS. 3 and 4 illustrate the concentrations of fluoride and arsenic when each is a function of time. The system uses chemical treatment to continuously operate for 4 hours to remove fluoride and arsenic. When thrown, the average flow into the system is 15.2 gpm. The average calcium chloride dose was 5 2.79 m 1 / m i η; the average sodium aluminate dose was 9.58 m 1 / m i η; the average iron chloride dose was 1.4 lml / mi η. The dose concentration of calcium chloride was 30%; the dose concentration of ferric chloride was 35%; the dose concentration of ΕΡ I-DM Α was 5%; the dose concentration of sodium aluminate was 38%. The information in Table 1 below shows that both the dilution and chemical treatments according to the present invention can reduce the arsenic and fluoride content to acceptable levels. (Please read the precautions on the back before filling out this page). 11-^ 1 The paper size printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 specification (210X29? Mm) -22- 548243 A7 B7 V. Description of the invention (20_ ---- Arsenic fluoride dilution treatment and dilution dilution treatment and release theory The theoretical maximum inlet concentration 10.8 1441-(ppm) The theoretical maximum outlet concentration 0.323-43.2 (ppm) The maximum maximum inlet concentration- 2.4-863.7 (ppm) Actual maximum export concentration-0.0136-6.06 (ppm) Reduced concentration by 97.0% 99.4% 97.0% 99.3% Recovered 0% 81.1% 0% 76.6% (Please read the precautions on the back before filling this page) Economy The Ministry of Intellectual Property Bureau employee consumer cooperative printed an improved method for removing arsenic and fluoride from an aqueous solution using the same process provided by the present invention as taught in the foregoing description and examples. The specific embodiment described previously and the present invention The examples are for the purpose of illustration and description. Although the present invention is illustrated with certain examples in progress, they are not to be interpreted and limited. They are not It is intended to clarify or limit the precise form of the present invention, and many modifications, embodiments, and alterations apparent from the above teachings are possible. The scope of the present invention is intended to include the general scope disclosed herein, and so far Additional applications are equivalent to them. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -23-