200840801 九、發明說明： 【發明所屬之技術領域】 相關申請案之交互參照 此申請案為2006年9月7曰申請之美國序號 1 1/5 16,843的部分接續申請案。包含在美國序號丨1/516,843 中之主題於此以參考方式併入本文。 本發明涉及一種經由使用浸沒式超微濾或微過濾薄膜 系統從都市廢水移除重金屬的方法。 【先前技術】 由於嚴謹的環境規章及/或水資源匱乏，一些城市必需 在排出或重複使用前從廢水移除重金屬。歐洲水資源架構 才日令（European Water Framew〇rk ㈣（2〇〇〇/6〇/EC)指 出未來排出物優先減低物質諸如重金屬。此規章以最大容 弁風險主要意義為主，其中排出至環境的化合物應該不會 或產生可忽略的環境或人類風險。此歐洲法規之荷蘭詮釋 L在稱號為4e nota Waterhuishuiding，，的國家法規中。 此法規尤其描述出未來地面水排出之金屬限制。來自此法 規的貝化例有下列可能的可溶金屬排出需求··鎘：〇.4 ppb、 5 PPb 鎳· 5· 1 ppb、錯：11 ppb、辞：9·4 ppb、鉻： 8·7 PPb及砷：25 PPb。現在，大部分含重金屬廢水藉由商 ⑽DTC/TTC化學藥品或特殊的聚合DTc化合物處理，然 後在》儿降槽中分離沉澱的金屬。於最近幾年中，超微濾（UF) 或U過濾（MF)膜已漸增地取代沉降槽而使用於固體液體分 6 200840801 離，因為UF/MF膜方法更精巧及產生具有比沉降槽更好的 品質之水，特別是幾乎無懸浮固體及可忽略的濁度。UF或 MF滲透液可重複使用且依重複使用的目的含或不含任何 進一步處理。因此，都市廢水當以聚合螯合劑處理及隨後 經UF或MF膜過濾時產生高金屬移除且亦產生比以商品 DTC/TTC/TMT化學藥品處理者還高的膜通量。 雖然已於此應用中使用交叉流UF或MF方法，這些 方法由於需要高交叉流能量來減低薄膜骯髒，其操作成本 通常高。在最近十年間或如此，浸沒式UF及MF膜已成 功地使用於高懸浮固體分離應用，諸如在薄膜生物反應器 (MBR)中；或低懸浮固體應用，諸如原水處理及三級處理。 在這些應用中，浸沒式薄膜以低通量（1〇_6〇 LMH)操作，因 為薄膜在較高通量下變骯髒。為了減少薄膜骯髒，使用通 氣來連續地（例如在MBR中）或間歇地（例如在MBR、原水 及二級處理中）洗滌薄膜表面。因此，有興趣的是對其它應 用（諸如重金屬移除）採用這些相當低操作成本之浸沒式薄 膜系統且與作用為金屬錯合劑和膜通量促進劑的聚合螯合 劑結合。聚合物螯合劑在過濾系統中的應用已在美國專利 案號5,346,627及6,258,277(其於此以參考方式併入本文） 中討論。 【發明内容】 本發明提供一種使用薄膜分離方法從都市廢水移除一 或多種重金屬的方法，其包括下列步驟：（a)將含重金屬的 200840801 都市廢水收集在合適於容納該都市廢水之儲槽中；（b)，敕 該系統的pH以在該都市廢水中達成重金屬之氣氧化物之 沉澱；（c)加入有效量可溶於水具有分子量從約5〇〇至約 10,000道耳吞的二氯乙烷氨聚合物，其包含約5至約5〇 莫耳百分比之二硫胺基曱酸鹽基團以與在該都市廢水系統 中的重金屬反應；（d)選擇性淨化來自步驟^之經處理的廢 水；（e)讓經處理的都市廢水通過一浸沒式薄膜，其中該浸 沒式薄膜為超微濾膜或微過濾膜；及（f)視需要反沖洗該薄 膜以從薄膜表面移除固體。 【實施方式】 名詞定義： ”UFn意謂著超微濾法。 f’MF”意謂著微過濾法。 DTC意谓者二硫胺基甲酸二甲醋。 ’TTCπ意谓著三硫碳酸鹽。 ΤΜΤ思谓者二疏基三明：。 "ΤΜΡ”意謂著透膜壓力。 "LMHn意謂著每平方公尺每小時的升數。 ’’通量π意謂著每單位時間每單位薄膜面積通過薄膜過 濾的水量。 ”都市廢水”意謂著來自集中型或分散型都市廢水處理 工廠的廢水。集中型水處理工廠包括來自家庭及工廠的廢 水刀政t水處理工薇包括來自處理自身廢水之集合住 8 200840801 宅、旅館、度假村及其類似地方的廢水。 •’螯合劑清除劑”意謂著能夠與螯合劑錯合的化合物。 這些清除劑通常為（但不限於）鹽形式。 π浸沒式薄膜’’意謂著完全浸沒在欲過濾之液體本體下 的薄膜。 η聚合螯合劑11意謂著與重金屬反應及/或錯合的聚合分 子0 ’’兩性聚合物”意謂著衍生自陽離子單體及陰離子單體 二者及可能其它非離子單體的聚合物。兩性聚合物可具有 甲正或負電荷。兩性聚合物亦可衍生自兩性離子單體及陽 離子或陰離子單體及可能非離子單體。此兩性聚合物可溶 於水。 發明之陽離子聚合物藉由聚合—或多種陽離子單體、藉由 t聚合—或多種非離子單體與-或多種陽離子單體、藉由 合表氣醇與二胺或聚胺或縮合二氯乙烯與氨或甲路及胺 鹽來製備。此陽離子聚合物可溶於水。 π兩性離子聚合物”音 〇 w明者由兩性離子單體及可能其它 非#子單體組成之繫人 人 Α 口物。在兩性離子聚合物中，全部聚 口物鏈及在鏈内的片段 子Ψ人腧α主 饭雉只地▼中性電。因此，兩性離 于來a物代表兩性聚合物 合物鏈S J4 π ^ 的支、、且，其必需在遍及全部的聚 口物鏈及片段中維持電荷中 内引進降離；+ 口為在相同兩性離子單體 Μ Μ進陰離子電荷及陽離 可溶於水。 何一者。此兩性離子聚合物 9 200840801 陰離子聚合物”意 萨明之降雜工取人 有疋體負電荷的聚合物。本 毛明之陰離子聚合物藉由聚合一 丘聚合一式夕括& a夕種陰離子單體或藉由 ，、承口 或多種非離子單體與一十> 備。纟、 或多種陰離子單體來製 m此陰離子聚合物可溶於水。 較佳的具邀實例: 如上述描述，本發明提供一 V7 JU i #使用浸沒式微過減膜或 浸沒式超微濾膜從都市廢水移 〜又'狀履膜次 若螯合劑存在於都市廢水5夕種重金屬的方法。 在都市廢水中的金屬與螯合劑去t則需要㈣PH以使 同步加入—或多種螯合劑清除劑錯且於此需要隨後或 劑通常將與金屬去錯合，將;JH小於4時’餐合 較佳。 _整在範圍從約3至約4 在一個具體實例中，螯合㈣、主 ^ ^ σ Μ凊除劑包括Ca或Mg或Α1 或Fe 〇 在另一個具體實例中，含p 下列所組成之群：氯化亞鐵、 e的螯合劑清除劑選自於由 或其組合 硫酸亞鐵、氯化鐵、硫酸鐵 可使用多種型式及量的酸及驗來調整都市廢水之阳。 在個具體實例中，鹼可選自於由鎂及鈣鹽，諸如氯 化物及氫氧化物，所組成之群。 在另個具體貫例中，鹼選自於由鈉、鉀、銨及其類 似物的氫氧化物所組成之群。 可使用多種鐵化合物及劑量來進一步處理pH值經調 整的都市廢水。在更另一個具體實例中，所使用的鐵化合 10 200840801 物之劑量可依存在於都市廢水中的螯合劑含量而從約i ppm 至約 1〇,〇〇〇 ppm。 /-從都市廢水系統移除重金屬的步驟為下列步驟：調 整系統之pH以在都市廢水中達成重金屬的氮氧化物^ 澱。當廢纟pH讓金屬氫氧化物具有最小溶解度時發生氣 氧化物沉澱。 在較佳的具體實例中’將都市廢水之pH提高至pH約 7至約1〇。都市廢水之pH值的調整依所存在的金屬而定。 已設想能冑pH調整至想要的範圍之任何驗。例如，_ 擇用於PH調整的驗選自於由納、钟m及其_ 似物的氫氧化物所組成之群。 在另一個具體實例中，欲從都市廢水移除的重金屬選 自於由下列所組成之群：Pb、CU、Zn、Cd、Ni、Hg、Ag、 Co、Pd、Sn、Sb、Ba、Be 及其組合。 二氯乙烷氨聚合物是藉由二氯乙烷與氨之反應來製 備。起始一氯乙烷氨聚合物通常具有分子量範圍5〇〇_ 100,000。在較佳的具體實例中，分子量為^00至1〇,〇⑽， 最佳的分子量範圍為1 5500_5,〇〇〇。用來製造這些聚合物的 典型反應描述在美國專利案號5,346,627中，其於此以參 考方式併入本文。聚合物亦可從Nalco公司，1601 West200840801 IX. INSTRUCTIONS: [Technical field to which the invention pertains] Cross-reference to related applications This application is a partial continuation application of US Serial No. 1 1/5 16,843, filed on September 7, 2006. The subject matter contained in U.S. Serial No. 1/516,843 is incorporated herein by reference. The present invention relates to a method of removing heavy metals from municipal wastewater via the use of submerged ultrafiltration or microfiltration membrane systems. [Prior Art] Due to stringent environmental regulations and/or lack of water resources, some cities must remove heavy metals from wastewater before they are discharged or reused. The European Water Resources Architecture (European Water Framew〇rk (4) (2〇〇〇/6〇/EC) indicates that future emissions will preferentially reduce substances such as heavy metals. This regulation is based on the main meaning of maximum tolerance risk, which is discharged to Environmental compounds should not or have negligible environmental or human risks. The Dutch interpretation of this European regulation is in the national regulations entitled 4e nota Waterhuishuiding, which specifically describes the metal limits for future surface water discharge. The Bayesian example of this regulation has the following possible soluble metal discharge requirements: · Cadmium: 〇.4 ppb, 5 PPb Nickel · 5· 1 ppb, Error: 11 ppb, Word: 9·4 ppb, Chromium: 8·7 PPb and arsenic: 25 PPb. Now, most of the heavy metal-containing wastewater is treated by commercial (10) DTC/TTC chemicals or special polymeric DTC compounds, and then the precipitated metal is separated in the Descending tank. In recent years, Supermicro Filtration (UF) or U-filter (MF) membranes have been increasingly used to replace settling tanks for solid liquids. 6 200840801, because the UF/MF membrane process is more compact and produces water with better quality than settling tanks, especially It is almost free of suspended solids and negligible turbidity. UF or MF permeate can be reused and with or without any further treatment for repeated use purposes. Therefore, municipal wastewater is treated with a polymeric chelating agent and subsequently via UF or MF. Membrane filtration produces high metal removal and also produces higher membrane flux than those of commercial DTC/TTC/TMT chemical processors. Although cross-flow UF or MF methods have been used in this application, these methods require high crossover Flow energy to reduce film fouling, which is generally expensive to operate. In the last decade or so, submerged UF and MF membranes have been successfully used in high suspended solids separation applications, such as in membrane bioreactors (MBR); or Low suspended solids applications, such as raw water treatment and tertiary treatment. In these applications, the submerged membrane operates with low flux (1〇_6〇LMH) because the membrane becomes dirty at higher fluxes. Dirty, using aeration to wash the surface of the film continuously (for example in MBR) or intermittently (for example in MBR, raw water and secondary treatment). Therefore, it is of interest to other applications (such as Metal removal) using these relatively low operating cost immersion film systems and in combination with polymeric chelating agents acting as metal chelators and membrane flux enhancers. The use of polymer chelators in filtration systems is available in US Patent No. The invention provides a method for removing one or more heavy metals from municipal wastewater using a membrane separation process, comprising the steps of: (a) Heavy metal-containing 200840801 municipal wastewater is collected in a tank suitable for containing the municipal wastewater; (b) 敕 the pH of the system to achieve precipitation of gaseous oxides of heavy metals in the municipal wastewater; (c) adding an effective amount a dichloroethane ammonia polymer having a molecular weight of from about 5 Torr to about 10,000 amps dissolved in water, comprising from about 5 to about 5 mole percent of a dithiol amide group to Heavy metal reaction in urban wastewater systems; (d) selective purification of treated wastewater from step; (e) passage of treated municipal wastewater through a submerged membrane, wherein the dip The non-type film is an ultrafiltration membrane or a microfiltration membrane; and (f) the membrane is backwashed as needed to remove solids from the surface of the membrane. [Embodiment] Noun definition: "UFn means ultrafiltration. f'MF" means microfiltration. DTC means dimethyl thioacetate. 'TTCπ means trisulphate. ΤΜΤ思说者二疏基三明:. "ΤΜΡ" means transmembrane pressure. "LMHn means the number of liters per square meter per hour. ''The flux π means the amount of water filtered per unit of membrane area per unit time through the membrane.” “Waste water” means wastewater from a centralized or decentralized municipal wastewater treatment plant. The centralized water treatment plant includes wastewater from the home and the factory. The water treatment unit includes a collection of domestic wastewater. 8 200840801 House, hotel Wastewater from resorts, resorts and the like. • 'Terrant remover' means a compound that is capable of intercalating with a chelating agent. These scavengers are typically, but not limited to, salt forms. The π immersion film '' means a film completely immersed under the liquid body to be filtered. The η-polymerizing chelating agent 11 means a polymeric molecule which reacts with and/or is misaligned with a heavy metal. The 0 ''amphoteric polymer' means a polymer derived from both a cationic monomer and an anionic monomer and possibly other nonionic monomers. The amphoteric polymer may have a positive or negative charge. The amphoteric polymer may also be derived from a zwitterionic monomer and a cationic or anionic monomer and possibly a nonionic monomer. The amphoteric polymer is soluble in water. By polymerizing - or a plurality of cationic monomers, by t-polymerization - or a plurality of nonionic monomers with - or a plurality of cationic monomers, by combining epigas alcohol with diamine or polyamine or by condensing dichloroethylene with ammonia or The cationic polymer is soluble in water. The π zwitterionic polymer is a human mouth composed of zwitterionic monomers and possibly other non-# monomers. In the zwitterionic polymer, all the polymer chains and the fragments in the chain are only neutral to the main rice cooker. Therefore, the amphoteric is a branch of the amphoteric polymer chain S J4 π ^ , and it must be introduced into the charge throughout the chain and the fragment; The same zwitterionic monomer Μ 阴离子 anion charge and cation are soluble in water. Which one. The zwitterionic polymer 9 200840801 anionic polymer "Italian" is a polymer with a negative charge of the steroid. The anionic polymer of the present invention is polymerized by polymerization. Or by, a socket or a plurality of nonionic monomers and a decimator, or a plurality of anionic monomers, the anionic polymer is soluble in water. Preferred examples: as described above, The invention provides a V7 JU i #Using a submerged micro-negative film or an immersed ultra-microfiltration membrane to remove heavy metals from urban wastewater into a municipal wastewater. The metal and the chelating agent are required to (4) the pH to be added simultaneously - or a plurality of chelating agent scavengers are wrong and the subsequent or the agent will usually be misaligned with the metal, and the JH is less than 4's better. The whole range is from about 3 to about 4. In one embodiment, the chelate (four), main ^^ σ decanting agent comprises Ca or Mg or Α1 or Fe 〇 in another specific example, comprising p : ferrous chloride, e chelating agent scavenger It is selected from the group consisting of ferrous sulfate, ferric chloride and ferric sulfate to adjust the cation of municipal wastewater using various types and amounts of acid. In a specific example, the base may be selected from magnesium and calcium salts. In a specific embodiment, the base is selected from the group consisting of hydroxides of sodium, potassium, ammonium, and the like. A variety of iron compounds can be used. And dosage to further treat pH adjusted urban wastewater. In still another embodiment, the dose of iron compound 10 200840801 used may range from about i ppm to about 1 依 depending on the amount of chelating agent present in the municipal wastewater. , 〇〇〇ppm. / - The step of removing heavy metals from the urban wastewater system is the following steps: adjusting the pH of the system to achieve heavy metal NOx in municipal wastewater. When the pH is reduced, the metal hydroxide is minimized. Precipitation of gas oxide occurs in solubility. In a preferred embodiment, the pH of the municipal wastewater is increased to a pH of from about 7 to about 1 Torr. The pH of the municipal wastewater is adjusted depending on the metal present. pH adjustment Any test of the desired range. For example, the test selected for pH adjustment is selected from the group consisting of hydroxides of nanometers, bells, and their likes. In another specific example, The heavy metal removed by the wastewater is selected from the group consisting of Pb, CU, Zn, Cd, Ni, Hg, Ag, Co, Pd, Sn, Sb, Ba, Be, and combinations thereof. The material is prepared by the reaction of dichloroethane with ammonia. The starting monochloroethane ammonia polymer usually has a molecular weight range of 5 〇〇 100,000. In a preferred embodiment, the molecular weight is 00 to 1 〇, 〇(10), the optimum molecular weight range is 1 5500_5, 〇〇〇. A typical reaction for the manufacture of these polymers is described in U.S. Patent No. 5,346,627, which is incorporated herein by reference. Polymers are also available from Nalco, 1601 West
Diehl Road，Naperville，IL· 購得。 二氯乙烧氨聚合物可以不同量加入。 在一個具體實例中，加入至都市廢水之可溶於水的二 氯乙纟元氨聚合物之有效量是從i ppm至約1〇,〇〇〇 活性 11 200840801 固體。 在另一個具體實例中，加入至都市廢水中之可溶於水 的二氯乙烷氨聚合物具有分子量約2,000至約2,〇〇〇,〇〇〇道 耳呑。 在另一個具體實例中，讓經處理的都市廢水通過浸沒 式薄膜之驅動力置為正或負壓力。 在另一個具體實例中，通過浸沒式微過濾膜或超微濾 膜之經處理的都市廢水可通過一或多個薄膜來進一步處 理。 在更進一步具體實例中，其它薄膜為逆滲透膜或奈米 過濾膜。 使用來處理含重金屬的都市廢水之浸沒式薄膜可具有 多種型式的物理及化學參數。 關於物理參數，在一個具體實例中，超微滤膜具有孔 洞尺寸範圍0·〇〇3至〇.丨微米。 在另一個具體實例中，微過濾膜具有孔洞尺寸範圍〇1 至10微米。 在另一個具體實例中，浸沒式薄膜具有選自於由下列 所組成之群的組態：中空纖維組態、平板組態或其組合。 在另一個具體實例中，薄膜具有螺捲組態。 在另個具體實例中，浸沒式薄膜具有毛細管組態。 關於化學參數，在-個具體實例中，浸沒式薄膜為聚 合物。 在另一個具體實例中，薄膜為無機物。 12 200840801 在更另-個具體實例中，薄膜為不錄鋼。 可對所主張的發明執行其它物理及化學薄膜參數。 在以可’合於水的一氯乙烷氨聚合物處理都市廢水後， 可以-或多種可溶於水的聚合物進一步處理此廢水以進一 步增加顆粒尺寸及提高膜通量。 在一個具體實例中，可溶於水的聚合物選自於由下列 所組成之群：兩性聚合物、陽離子聚合物、陰離子聚合物、 兩性離子聚合物及其組合。Diehl Road, Naperville, IL·. The dichloroethylene carbonated amino polymer can be added in varying amounts. In one embodiment, the effective amount of the water-soluble dichloroethylidene ammonia polymer added to the municipal wastewater is from i ppm to about 1 Torr, 〇〇〇 activity 11 200840801 solids. In another embodiment, the water-soluble dichloroethane ammonia polymer added to the municipal wastewater has a molecular weight of from about 2,000 to about 2, 〇〇〇, 呑 呑. In another embodiment, the treated municipal wastewater is subjected to a positive or negative pressure by the driving force of the submerged film. In another embodiment, the treated municipal wastewater passing through the submerged microfiltration membrane or ultrafiltration membrane can be further processed by one or more membranes. In still further embodiments, the other film is a reverse osmosis membrane or a nanofiltration membrane. Submerged membranes used to treat municipal wastewater containing heavy metals can have a variety of physical and chemical parameters. Regarding the physical parameters, in one embodiment, the ultrafiltration membrane has a pore size ranging from 0·〇〇3 to 〇.丨micron. In another embodiment, the microfiltration membrane has a pore size ranging from 〇1 to 10 microns. In another embodiment, the submerged film has a configuration selected from the group consisting of: a hollow fiber configuration, a plate configuration, or a combination thereof. In another embodiment, the film has a spiral configuration. In another embodiment, the submerged membrane has a capillary configuration. Regarding the chemical parameters, in a specific example, the immersion film is a polymer. In another embodiment, the film is an inorganic material. 12 200840801 In a further specific example, the film is not recorded. Other physical and chemical film parameters can be performed on the claimed invention. After the municipal wastewater is treated with a water-soluble monochloroethane ammonia polymer, the wastewater can be further treated with or - a plurality of water-soluble polymers to further increase the particle size and increase the membrane flux. In one embodiment, the water soluble polymer is selected from the group consisting of amphoteric polymers, cationic polymers, anionic polymers, zwitterionic polymers, and combinations thereof.
在另一個具體實例中，可溶於水的聚合物具有分子量 從10,000至約2,000,000道耳呑。 在另一個具體實例中，兩性聚合物選自於由下列所組 成之群··丙烯酸二曱基胺基乙酯氯甲烷四級鹽 (DMAEA.MCQ)/丙烯酸共聚物、氯化二烯丙基二甲基銨/丙 烯酸共聚物、丙烯酸二甲基胺基乙酯氯甲烷鹽/N，N_二曱基 甲基丙烯醯胺基丙基_N-(3_磺丙基）_銨甜菜鹼共聚物、 丙烯酸/N，N-二曱基曱基丙烯醯胺基丙基-N-(3-確丙基）· 銨甜菜鹼共聚物、及DMAEA.MCQ/丙烯酸/N，N-二甲基七 甲基丙烯醯胺基丙基-N-(3-磺丙基銨甜菜鹼三聚物。 在另一個具體實例中，兩性聚合物的劑量從約i a Ail 至約2000 ppm活性固體。 在另一個具體實例中，兩性聚合物具有分子量約5 〇⑽ 至約2,000,000道耳呑。 在另一個具體實例中，兩性聚合物具有陽離子電荷者 量對陰離子莫耳電荷當量之比率為約3·0 ·· 7.〇至約9田 13 200840801 0·2。 在另一個具體實例中，陽離子聚合物選自於由下列所 組成之群：聚氯化二烯丙基二曱基銨（聚DADMAC)、聚乙 烯亞胺、聚表胺（polyepiamine)、與氨或乙二胺交聯的聚表 胺、二氯乙烯與氨之縮聚物、三乙醇胺與妥爾油脂肪酸之 縮聚物、聚（二曱基胺基乙基甲基丙烯酸酯硫酸鹽）及聚（二 甲基胺基乙基丙浠酸酯氣曱烧四級鹽）。 在另一個具體實例中，陽離子聚合物為丙烯醯胺（AcAm) 與一或多種選自於由下列所組成之群的陽離子單體之共聚 物：氯化二烯丙基二曱基銨、二甲基胺基乙基丙烯酸酯氯 甲烷四級鹽、二曱基胺基乙基曱基丙烯酸酯氯甲烷四級 鹽、及二曱基胺基乙基丙烯酸酯苄基氣四級鹽 (DMAEA.BCQ)。 在另一個具體實例中，陽離子聚合物的劑量為約Q1 ppm至約1000 ppm活性固體。 在另個具體貫例中，陽離子聚合物具有至少2莫耳 百分比之陽離子電荷。 在另—個具體實例中，陽離子聚合物具有100莫耳百 分比的陽離子電荷。 在另一個具體實例中，陽離子聚合物具有分子量約 2.000 至約 10,000,000 道耳吞。 在另一個具體實例中，陽離子聚合物具有分子量約 20.000 至約 2,〇〇〇,〇〇〇 道耳呑。 在另-個具體實例中，兩性離子聚合物是由約1至約 14 200840801 99莫耳百分比的N，N•二甲基甲基丙烯醯胺基兩基 磺丙基）-銨甜菜鹼及約99至約1莫耳百分比的一或多種非 離子單體組成。 可選擇性淨化來自步驟c之經處理的廢水。 可使用多種型式的薄膜分離方法。 在一個具體實例中，薄膜分離方法選自於由下列所組 成之群·交叉流薄膜分離方法，即，以連續通氣來洗務薄 _ 膜；半端點流薄膜分離方法，即，以間歇通氣來洗滌薄膜； 及端點流薄膜分離方法，即，無通氣來洗滌薄膜。 可能的都市廢水處理方案顯示在第2圖中。 參知弟1圖’將含重金屬的都市廢水收集在儲槽（1)中， 其中經由管線（3)加入酸或鹼以將pH調整至3-4。然後經 由管線（3 A)加入螯合劑清除劑諸如鐵化合物。然後讓此水 流至儲槽（2)，其中經由線上（in-line)(4)或直接（5)添加鹼到 儲槽（2)中將pH調整至8-10。然後讓水從儲槽（2)流至已浸 _ 沒超微濾或微過濾膜（1 0)的儲槽（8)。可對超微渡或微過濾 膜施加通氣。可線上（6)或直接（9)將聚合螯合劑諸如二氯乙 烧氨聚合物加入薄膜槽（8)中。在加入二氣乙烷氨聚合物 後’在水流入薄膜槽（8)前可選擇性於線上（7)加入一或多種 可溶於水的聚合物。來自浸沒式超微濾或微過濾膜方法之 今透液（11)可藉由讓渗透液通過其它薄膜（12)選擇性處理， 及丟棄物（濃縮物）（13)可送至進一步除水或抛棄。 下列實施例不意欲限制所主張的發明之範圍。 實施例 15 200840801 在藉由原廢水之低負載硝化/脫氮活化泥漿方法及隨後 淨化之原廢水處理之後，獲得經二級處理的廢水。從當地 城市獲得之經二級處理的廢水包含17 ppb Zn、3.1 ppb Cu 及 1.99ppbNi。此廢水以 10-20ppm二氯乙烷氨（EDC·NH3) 聚合物處理，在沉降槽中沉澱，然後讓經淨化的水過濾過 浸沒式中空纖維UF薄膜。此方法由第2圖闡明。接著UF 後都市廢水之EDC-NH3聚合物處理比起單獨的UF而言在 金屬移除上產生明顯的改良。 【圖式簡單說明】 第1圖闡明用來處理含重金屬之都市廢水的一般製程 方案，其包括浸沒式微過濾膜/超微濾膜和用來進一步處理 來自浸沒式微過濾膜/超微渡膜之滲透液的其它薄膜。 第2圖闡明廢水的一般製程方案，其以丨〇-2〇 ppm二 氯乙烧氨（EDC-NH3)聚合物處理，在沉降槽中沉澱然後讓 經淨化的水過濾過浸沒式中空纖維UF薄膜。 【主要元件符號說明】 1 儲槽 2 儲槽 3 管線 3A 管線 4 驗的添加 5 驗的添加 200840801 6 聚合螯合劑的添加 7 聚合物的添加 8 儲槽 9 聚合螯合劑的添加 10 微過濾膜 11 渗透液 12 薄膜 13 濃縮物 ⑩ 17In another embodiment, the water soluble polymer has a molecular weight of from 10,000 to about 2,000,000 deaf. In another embodiment, the amphoteric polymer is selected from the group consisting of: didecylaminoethyl chloromethane quaternary ammonium salt (DMAEA.MCQ)/acrylic acid copolymer, diallyl chloride Dimethylammonium/acrylic acid copolymer, dimethylaminoethyl acrylate methyl chloride/N,N-dimercaptomethylpropenyl propyl-N-(3-sulfopropyl)-ammonium betaine Copolymer, acrylic acid/N,N-dimercaptodecyl acrylamidopropyl-N-(3- propyl)·ammonium betaine copolymer, and DMAEA.MCQ/acrylic acid/N,N-dimethyl Heptamethyl methacrylamidopropyl-N-(3-sulfopropylammonium betaine terpolymer. In another embodiment, the amphoteric polymer is dosed from about ia Ail to about 2000 ppm active solids. In another embodiment, the amphoteric polymer has a molecular weight of from about 5 〇 (10) to about 2,000,000 Torr. In another embodiment, the amphoteric polymer has a ratio of cationic charge to anionic molar charge equivalent of about 3.8. ·· 7. 7.到到9田13 200840801 0·2. In another embodiment, the cationic polymer is selected from the group consisting of Polydiallyldimethylammonium chloride (polyDADMAC), polyethyleneimine, polyepiamine, polyamine linked with ammonia or ethylenediamine, polycondensate of dichloroethylene and ammonia, a polycondensate of triethanolamine and tall oil fatty acid, poly(didecylaminoethyl methacrylate sulfate) and poly(dimethylaminoethylpropionate gas sulphide quaternary salt). In another embodiment, the cationic polymer is a copolymer of acrylamide (AcAm) and one or more cationic monomers selected from the group consisting of diallyldimethylammonium chloride, dimethyl Aminoethyl acrylate chloromethane quaternary salt, didecylaminoethyl methacrylate chloromethane quaternary salt, and dimethylaminoethyl acrylate benzyl quaternary salt (DMAEA.BCQ In another embodiment, the cationic polymer is present in an amount from about Q1 ppm to about 1000 ppm active solids. In another specific embodiment, the cationic polymer has a cationic charge of at least 2 mole percent. In a specific example, the cationic polymer has a cation percentage of 100 moles In another embodiment, the cationic polymer has a molecular weight of from about 2.000 to about 10,000,000 argon. In another embodiment, the cationic polymer has a molecular weight of from about 20.000 to about 2, 〇〇〇, 〇〇〇道耳In another embodiment, the zwitterionic polymer is from about 1 to about 14 200840801 99% molar percentage of N,N•dimethyl methacrylamide amide-based sulfopropyl)-ammonium betaine And a composition comprising from about 99 to about 1 mole percent of one or more nonionic monomers. The treated wastewater from step c can be selectively purified. A variety of types of membrane separation methods can be used. In one embodiment, the membrane separation method is selected from the group consisting of: a cross-flow membrane separation method consisting of continuous venting to remove membranes; a semi-terminal flow membrane separation method, ie, intermittent ventilation The film is washed; and the end flow film is separated, that is, the film is washed without aeration. A possible urban wastewater treatment plan is shown in Figure 2. Referring to Figure 1, the heavy metal-containing municipal wastewater is collected in a storage tank (1), wherein an acid or a base is added via line (3) to adjust the pH to 3-4. A chelating agent scavenger such as an iron compound is then added via line (3A). This water is then allowed to flow to the storage tank (2) where the pH is adjusted to 8-10 by adding alkali to the storage tank (2) via in-line (4) or direct (5). The water is then allowed to flow from the reservoir (2) to a reservoir (8) that has been immersed _ without ultrafiltration or microfiltration membrane (10). Ventilation can be applied to the ultrafine or microfiltration membrane. A polymeric chelating agent such as a dichloroethane ammonia polymer can be added to the film tank (8) either on line (6) or directly (9). After the addition of the di-ethane ethane ammonia polymer, one or more water-soluble polymers may be selectively added to the line (7) before the water flows into the film tank (8). The liquid permeation (11) from the immersed ultrafiltration or microfiltration membrane method can be further removed by allowing the permeate to be selectively treated by other membranes (12) and discards (concentrates) (13). Or discard. The following examples are not intended to limit the scope of the claimed invention. Example 15 200840801 A secondary treated wastewater was obtained after the low-load nitrification/denitrification activated mud process of the raw wastewater and the subsequent purification of the raw wastewater. The secondary treated wastewater from the local city contains 17 ppb Zn, 3.1 ppb Cu and 1.99 ppb Ni. This waste water was treated with 10-20 ppm of dichloroethane ammonia (EDC·NH3) polymer, precipitated in a settling tank, and then the purified water was filtered through a submerged hollow fiber UF film. This method is illustrated by Figure 2. The EDC-NH3 polymer treatment of UF post-urban wastewater then resulted in significant improvements in metal removal compared to UF alone. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates a general process for treating municipal wastewater containing heavy metals, including submerged microfiltration membranes/ultrafiltration membranes and for further processing from submerged microfiltration membranes/supermicro membranes. Other films of permeate. Figure 2 illustrates the general process of wastewater treatment, which is treated with 丨〇-2〇ppm dichloroethane ammonia (EDC-NH3) polymer, precipitated in a settling tank and then filtered to purify the immersed hollow fiber UF. film. [Main component symbol description] 1 Storage tank 2 Storage tank 3 Pipeline 3A Pipeline 4 Addition of test 5 Addition of test 200840801 6 Addition of polymerization chelating agent 7 Addition of polymer 8 Storage tank 9 Addition of polymerization chelating agent 10 Microfiltration membrane 11 Permeate 12 film 13 concentrate 10 17