200838809 九、發明說明： 【發明所屬之技術領域】 本么月疋有關於-種化學氧化的水處理法，特別是有關 於-種·顏化床枝，喊少水中鐵、龄泥含量的處 理法。本發明適宜處理含鐵、鐘量過高的地下水、工業用水 等領域。 【先前技術】 P現著工業的日益發達，許多的工業用水必須先經過氧 化、混凝和猶程序處理減少水中鐵、鐘的含量後，方可達 到工業用水鮮；修_添加高峨鉀為氧化劑，氧化水 中的二價鐵離子或二價_子，使產生不溶性的氯氧化鐵或 缝’私混凝和顯程序降低水巾關度或色度，是 、¥見的方法之’但其缺點在於會產生大量的化學污 泥’這些3泥雖然可用沈職或浮除設備加以分離，但會造 成用地需求上的錢及雌生污泥處置上的隨；另^ 面，隨著都市的發展與人口的日漸密集，用水的需求日增， 欠疋重要的用水來源之_，但有些地下水含鐵、鐘量過 高，需做適當的祕財適錢用，傳統的綠是利用曝氣 並外加混凝鍾絲水额㈣麵、歸，触法和上述 添加高鐘酸鉀方法的共同缺點有：⑴水力停留時間長··通常 200838809 大於3小4 ’⑵佔地面積大：沈殺槽溢流率通常小於〗m/hr， =即處理每天1__水量之沈殿槽佔地面積需大洲心⑶ π泥4里大·沈殿槽中污泥含水率—般大於搬，需後續濃 f、脫水設施，即使經濃縮、脫水後其含水率仍大於，這 是既有處理技術的缺點。 【發明内容】200838809 IX. Description of the invention: [Technical field to which the invention belongs] This month, there is a water treatment method for chemical oxidation, especially for the treatment of the species, the bed, the shouting of iron and the age of mud. law. The invention is suitable for the fields of iron, high groundwater, industrial water and the like. [Prior Art] P is now an increasingly developed industry. Many industrial waters must be oxidized, coagulated, and treated to reduce the content of iron and clock in water before they can reach industrial water fresh. An oxidizing agent that oxidizes divalent iron ions or divalent _ sub in water, so that insoluble iron oxychloride or sewn 'private coagulation and visible procedures reduce the degree or color of the water towel, is the method of seeing 'but its The disadvantage is that a large amount of chemical sludge will be produced. 'These 3 muds can be separated by the use of sinking or floating equipment, but they will cause the money on the land demand and the disposal of the female sludge; the other side, along with the urban Development and population are becoming increasingly dense, the demand for water is increasing, and the important source of water is owed. However, some groundwater contains iron and the amount of time is too high. It is necessary to make appropriate money for the use of money. The traditional green is to use aeration. And the addition of coagulation clock wire water (four) surface, return, touch method and the above-mentioned method of adding high potassium acid potassium have the following disadvantages: (1) long hydraulic retention time · usually 200838809 is greater than 3 small 4 ' (2) large area: sinking trough The overflow rate is usually small 〗 m / hr, = that is to deal with the daily amount of 1__ water in the Shen Dian trough area needs Dazhou heart (3) π mud 4 Li Da · Shen Dian tank sludge moisture content - generally greater than moving, need to follow the thick f, dehydration facilities, even if After concentration and dehydration, the water content is still greater than that, which is a disadvantage of the existing treatment technology. [Summary of the Invention]
點目的乃是要改善上述傳統混凝除鐵、錘法之缺 曰^降低水力停留咖、減少佔地面積並大幅 明之方法乃是利用流體化床結晶方法， 產出，在習^7枯、龜去除率和降低處理程序的污泥 水中的11二技中已有利用流體化床的方式來去除 中的重金屬’例如在美國專利us 476撕中，利 以與重金屬反應，以流體化床方式 ，磁鹽結晶；另在美國專利us 疋利用驗金屬硫化物與重金屬反應式 (〇2)與二價鐵、錳離L ί則疋利用水中的氧 曰i由：二：：床方式獲得此鐵，氧化物的錄 日日由於、、，口日日的含水率不高（小於1〇 到降低污泥產量的目的·箕冰，并▲ )各Ί以逆 點，可在低水力停丨卜^概床充分混合的優 行，提昇鐵m小佔地面積下，促錄化反應的進 【實施方式】 祀康述目的，本發明所提供之水處理方法包括下列资 4 200838809 驟·將含一價鐵、！孟離子之水溶液預先調整好阳健，引 進y流體化床反應槽中，使之與水中的(〇2)充分混合反 應；其中上述之流體化床反應槽中具有適當之擔體，可以使反 應所生成的高價鐵、鐘氧化物大部份得以結晶披覆在擔體表面 上，之後，將處理過之水移出此反應槽。 、以下將配合第1圖，就本發明之化學氧化水處理 法，作一詳細說明。 第j，為說明本發明之裝置示意圖，其中2為原水貯 • 槽，4為氧貯槽，6為二價鐵、錳貯槽，10為流體化床反應 槽，η為擔體，21、23、25為管路，12、14、16、 18為泵浦。 本發明之方法是在一流體化床反應槽1〇中進行， 而此反應槽中外接有迴流水迴路Μ，可使反應槽中的部份水 迴流，而使擔體流體化。 首先，將適當的擔體Π置入反應槽中，適當的擔體 顆粒將可使反應後所生成的高價鐵、錳化合物結晶在 其上。其次’將原水聍槽2中調整好pH值的水經由 _ 管路21注入反應槽10中，並啟動迴流泵18，依所使用 擔體的種類和粒徑控制適當的上流速度，使擔體j i 流體化。適當的顆粒擔體包括蹲粉、活性碳、氧化鋁、 矽砂、矽藻土、玻璃、合成樹脂、輕浮石（pumic)、及 人造顆粒等；適當的上流速度約在10420 ^心之 間，以24-42 mesh的矽砂擔體為例，其適當的上流 速度在30-60 m/hr之間。 接著，將貯槽4、6中的氧與二價鐵、錳溶液由 反應槽10的底部注入，以進行化學氧化反應。例如 二價鐵、錳溶液可先打入迴流管，與迴流水充分混 200838809 合，如此可避免局部濃度過高而影響化學氧化反應， 此股水再由槽體底端進料，以和氧充分混合，並在擔 體表面披覆上鐵、錳氧化物，其中氧的來源可為水中 的溶氧或由氧氣、空氣提供。 之後，在反應槽ίο中控制適當的水力停留時間 和面積負荷，使反應後產生的高價鐵、錳多數於擔體 11的表面進行結晶於擔體上，以降低程序的污泥產 量，而處理後之水可由反應槽的頂部流出。依照本發 明，pH的範圍以6-9之間較佳，適當的水力停留時間 為6-60分鐘。 此外，反應完成後的鐵、錳氧化物結晶可從擔體 上分離，如此擔體可以回收再使用。 依據本發明之水處理法的應用領域相當廣泛，包 括：（1)染整業、人造纖維、紡織業、石化、化工、造 紙業等用水；（2)飲用水；以及(3)地下水等。 為讓本發明之上述和其他目的、特徵、和優點能 更明顯易懂，下文特舉出較佳實施例，作詳細說明如 下。 實施例1 在本實施例中，是以矽砂作為流體化床的擔體，依上 述方法對不含有機物之入流水（總有機碳TOOO mg/L)進行處理，其詳細之操作條件與處理結果如表 1所示： 200838809 表1含20.0 mg/L鐵、2.0 mg/L锰水溶液在流體化床中反應Ihr 的處理效果 操作條件 出流水處理結果 總锰 錳污泥 總鐵 鐵污泥 pHi 溶氧 濃度 減少率 濃度 減少率 (mg/L) (mg/L) (%) (mg/L) (%) 7.0 5.6 0.227 88.6 0.532 97.3 8.0 5.7 0.227 88.6 0.532 973 9.0 6.0 0.030 98.5 1.332 933 _ 由上表可知，利用流體化床的方式，在適當的 pH值下可使化學氧化法所產生之鐵、錳污泥產量分 別減少93%和88%以上。本發明之方法具有以下優 點： (1) 使用流體化床方式，可避免傳統混凝沈澱或 浮除法加藥不均所造成的藥品浪費。 (2) 由於化學氧化法反應所產生的大部份鐵、錳 氧化物在反應槽中截流5不再產生高價鐵、錳氧化物污 泥，使處理程序化學污泥產量降低，減少總污泥產量 • 88%以上。 (3) 水力停留時間短、佔地面積小。 雖然本發明已以較佳實施例揭露如上，然其並 非用以限定本發明，任何熟習此技藝者，在不脫離本 發明之精神和範圍内，當可作各種之更動與潤飾，因 此本發明之保護範圍當視後附之申請專利範圍所界 定者為準。 200838809 【圖式簡單說明】 2為原水貯槽 4為供氧貯槽 6為二價鐵、錳貯槽 10為流體化床反應槽 11為顆粒擔體 12、14、16、18 為泵浦 21、23、25為管路 【主要元件符號說明】The purpose of the above-mentioned purpose is to improve the above-mentioned conventional coagulation and iron removal, the lack of hammer method, reduce the hydraulic retention, reduce the floor space and make a large-scale method by using fluidized bed crystallization method, output, in the ha Turtle removal rate and sludge treatment in reducing sludge in the treatment program have been used to remove heavy metals in the form of a fluidized bed. For example, in the US patent us 476 tear, to react with heavy metals, in a fluidized bed manner. , magnetic salt crystallization; another US patent us 疋 use metal sulfide and heavy metal reaction formula (〇 2) and ferrous iron, manganese from L ί 疋 use water in the water 曰 i by: two:: bed way to obtain this The iron and oxide are recorded on the day of the day, and the moisture content of the mouth is not high (less than 1 〇 to the purpose of reducing sludge production, 箕冰, and ▲), each of which is reversed, and can be stopped at low hydraulic power. The best way to fully mix the bed, improve the iron m small footprint, and promote the recording reaction [embodiment] The purpose of the water treatment method provided by the present invention includes the following capital 4 200838809 With a price of iron,! The aqueous solution of Meng ion is pre-adjusted to Yangjian, and introduced into the reaction tank of y fluidized bed to make it fully mixed with water (〇2); wherein the fluidized bed reaction tank has appropriate support to make the reaction Most of the generated high-priced iron and bell oxide are crystallized on the surface of the support, and then the treated water is removed from the reaction tank. The chemical oxidation water treatment method of the present invention will be described in detail below with reference to Fig. 1. Chapter j is a schematic view of the apparatus of the present invention, wherein 2 is a raw water storage tank, 4 is an oxygen storage tank, 6 is a ferrous iron and manganese storage tank, 10 is a fluidized bed reaction tank, and η is a support, 21, 23, 25 is the pipeline, and 12, 14, 16, and 18 are pumps. The method of the present invention is carried out in a fluidized bed reaction tank, in which a reflux water circuit is externally connected, and a part of the water in the reaction tank is refluxed to fluidize the support. First, an appropriate support crucible is placed in the reaction tank, and appropriate support particles can crystallize the high-valent iron and manganese compounds formed after the reaction. Next, 'the pH-adjusted water in the raw water tank 2 is injected into the reaction tank 10 via the _ line 21, and the reflux pump 18 is started, and the appropriate upflow speed is controlled according to the type and particle size of the used carrier to make the support Ji fluidized. Suitable granule supports include strontium powder, activated carbon, alumina, strontium sand, diatomaceous earth, glass, synthetic resin, pumic, and artificial particles; the appropriate upstream velocity is about 10,420 ^ Å, Take the 24-42 mesh lining carrier as an example, and the appropriate upstream speed is between 30-60 m/hr. Next, oxygen in the storage tanks 4, 6 and a solution of ferrous iron and manganese are injected from the bottom of the reaction tank 10 to carry out a chemical oxidation reaction. For example, the ferrous iron and manganese solution can be firstly injected into the reflux pipe and mixed with the reflux water at 200838809. This can avoid the local concentration being too high and affecting the chemical oxidation reaction. This feed water is then fed from the bottom end of the tank to oxygen. It is thoroughly mixed and coated with iron and manganese oxide on the surface of the support. The source of oxygen can be dissolved oxygen in water or supplied by oxygen or air. Thereafter, the appropriate hydraulic retention time and area load are controlled in the reaction tank ί, so that the high-priced iron and manganese generated after the reaction are mostly crystallized on the surface of the support 11 to reduce the sludge yield of the process, and the treatment is performed. The latter water can flow out from the top of the reaction tank. In accordance with the present invention, the pH range is preferably between 6 and 9, with a suitable hydraulic retention time of from 6 to 60 minutes. Further, the iron and manganese oxide crystals after completion of the reaction can be separated from the support, so that the support can be recycled and reused. The water treatment method according to the present invention has a wide range of applications, including: (1) water dyeing and finishing, man-made fibers, textiles, petrochemicals, chemicals, papermaking, etc.; (2) drinking water; and (3) groundwater. The above and other objects, features, and advantages of the present invention will become more apparent and understood. Example 1 In this example, cerium was used as a support for a fluidized bed, and the inflow water (total organic carbon TOOO mg/L) containing no organic matter was treated according to the above method, and the detailed operating conditions and treatments were carried out. The results are shown in Table 1: 200838809 Table 1 contains 20.0 mg / L iron, 2.0 mg / L manganese aqueous solution in the fluidized bed reaction Ihr treatment effect operating conditions outflow water treatment results total manganese manganese sludge total iron iron sludge pHi Dissolved oxygen concentration reduction rate Concentration reduction rate (mg/L) (mg/L) (%) (mg/L) (%) 7.0 5.6 0.227 88.6 0.532 97.3 8.0 5.7 0.227 88.6 0.532 973 9.0 6.0 0.030 98.5 1.332 933 _ From It can be seen that the utilization of the fluidized bed can reduce the yield of iron and manganese sludge produced by the chemical oxidation method by 93% and 88%, respectively, at an appropriate pH value. The method of the invention has the following advantages: (1) The fluidized bed method can avoid the waste of medicine caused by the traditional coagulation sedimentation or the uneven addition of the floating method. (2) Due to the large amount of iron and manganese oxides generated by the chemical oxidation reaction, the high-temperature iron and manganese oxide sludge is no longer produced in the reaction tank, which reduces the production of chemical sludge and reduces the total sludge. Production • Over 88%. (3) The hydraulic retention time is short and the floor space is small. While the present invention has been described above by way of a preferred embodiment, it is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application. 200838809 [Simple description of the diagram] 2 is the raw water storage tank 4 is the oxygen storage tank 6 is divalent iron, the manganese storage tank 10 is the fluidized bed, the reaction tank 11 is the particle carrier 12, 14, 16, 18 is the pump 21, 23, 25 is the pipeline [main component symbol description]
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