201002629 六、發明說明： 【發明所屬之技術領域】 本發明於透過脫氮8將被處理水中含有的確酸離 子、亞頌祕子衫成11的脫氮處理方法域氮處理裝置。 近年來，在水處理的領域、特別是排水處理的領域中， 大多使用透過利用微生物的生理活性將排水中的污濁物質 變化爲無害的物質來進行處理的生物化學水處理。一般而 言，作為生物處理法，活性污泥法係為主流，但是在通常 的活性污泥法中，由於槽内微生物濃度的高濃度化較為困 難，不能較佳的取得負載，因此存在需要較大的占地面積、 生物的管理較難、容易產生膨脹等處理性能惡化、需要大 规模的沉澱設備、剩餘污泥等廢棄物產生量較多等問題。 爲了解决這些問題的技術，開發出透過膜進行活性污泥的 固液分離的方法、透過附著海綿或高分子載體等微生:來 進行處理的方法、利用微生物自己造粒的比重較 即利用顆粒進行處理的方法等。其中，使用顆:：爲 了在槽内保持多量的微生物，每單位體積的反應速度較 快’固液分離也比較容易，因此較被關注。 :π此，適用生物化學水處 ’在好氧性條件下，201002629 VI. Description of the Invention: [Technical Field] The present invention is a nitrogen treatment apparatus for denitrification treatment in which the acid ions and the scorpion scorpion shirt contained in the water to be treated are subjected to denitrification. In recent years, in the field of water treatment, particularly in the field of wastewater treatment, biochemical water treatment which treats a dirty substance in a wastewater by using a physiological activity of a microorganism to be harmless is often used. In general, the activated sludge method is the mainstream in the biological treatment method. However, in the conventional activated sludge method, it is difficult to obtain a high concentration of the microorganism concentration in the tank, and it is not possible to obtain a load. Large floor space, biological management is difficult, and processing performance such as swelling is likely to be deteriorated, and large-scale sedimentation equipment and excess sludge are required to generate a large amount of waste. In order to solve these problems, a method of performing solid-liquid separation of activated sludge through a membrane, a method of processing by micro-production such as adhesion of a sponge or a polymer carrier, and a method of using a microorganism to granulate itself are utilized. The method of processing, etc. Among them, the use of:: in order to maintain a large amount of microorganisms in the tank, the reaction rate per unit volume is faster, the solid-liquid separation is also relatively easy, so it is more concerned. : π this, apply to biochemical waters ‘under aerobic conditions,
在含有氮的排水處理中也是如此 理。例如，作爲含氨性氮的排水處理有 透過氨氧化細菌及亞硝酸 酸離子、硝酸離子之後， 3 201002629 件下，透過脫氮菌將亞硝酸離子、硝酸離子還原爲氮氣的 方=。此時，作爲氫供體，雖然能夠利用在排水中含有的 有枝物等，但是在氫供體不足的情况下，需要從外部供應。 此呀，氫供體以排水中的氮濃度爲基礎來决定供應量，並 基於該供應量連續地添加氫供體。 其中，在透過脫氮菌將亞硝酸離子、硝酸離子還原爲 氮氣的脫氮處理中，除了活性污泥法以外，有爲了提高脫 氮菌）辰度並且使固液分離容易而添加海錦或凝膠狀的載 體，來進行脫氮處理的方法。並且，還有透過脫氮菌本身 被自己造粒，形成比重較高的塊，即形成顆粒，顯著提高 槽内脫氮菌的濃度，來進行脫氮處理的方法。在使用顆粒 化的脫氮菌的處理方法中，爲了能夠將高濃度的脫氮菌保 持在槽内，槽的處理速度與添加載體的處理方法相較其速 度較快’由於不需要載體，能夠低成本化。此外，由於顆 粒的比重較高並且沉積速度較快，具有固液分離容易等優 點。如此顆粒的形成，以厭氧性曱烷醱酵、上流式污泥層 反應器(upflow sludge blanket reactor) (XJSB)杜"弋反 應器（sequencing batch reactor) ( SBR)來違行確，（例士， 參照專利文獻1至3)。 〜 專利文獻1 :日本特開昭63_258695銳公孝艮 專利文獻2:日本特開平1_262996號公報 專利文獻：3 :日本特開2〇〇〇_51893鏡公极 【發明内容】 4 201002629 發明所欲解决之問題 在批次式反應器中’脫氣槽爲完全混合型的，在一個 脫氮槽中，經過被處理水的流入、氧氣供應及被處理水與 脫氮菌的接觸、脫氮菌的沉積、處理水的排出這四個程序 來進行處理。但是，由於被處理水的流入和處理水的排出 都以短時間來進行，因此處理流量的變動變大，裝置中需 要大流量調整槽。因此，雖然在小規模裝置中因爲簡便而 成爲有利的裝置，但是難以適用於中〜大規模的裝置。並 且，在使用上流式污泥層反應器的情况下，雖然獲得非常 高的處理速度，但是由於使用特殊形狀的脫氮槽，因此設 備成本變高。並且，在裝置的構成上，由於不能夠充分進 行脫氮槽内部的攪拌，因此被處理水的pH控制變得困難， 在含有約等的被處理水中，具有産生水垢和顆粒中積蓄無 機物等問題。 爲了解决這樣的問題，期望利用目前在多數裝置中使 用的完全混合型脫氮槽，而使被處理水連續流入（以及連 續排出）的裝置構成，但是到目前爲止，沒有關於這樣裝 置構成中的脫氮菌顆粒形成報告。 因此，本發明之目的在於，在透過脫氮菌將被處理水 中含有的硝酸離子、亞硝酸離子還原成氮的脫氮處理中， 在使被處理水連續流入完全混合型的脫氮槽内，同時使脫 氮菌顆粒化。 解决技術問題的技術方案 5 201002629 本發明的脫氮處理方法，左 全混合魏IUf，贿理水連續供應給完 才i、應虱供體，透過脫氮菌將被處理 水^含有的賴離子、亞石肖_子還原成氮，Μ，_ 脫氮槽内被處理水的水力學彳哀毡士 …子間中脫氮槽内的氫供體 很度1M得1化的方式，並且㈣水 氮槽内氫供體的最大濃度與最小濃度的差成爲誘 菌自己造粒化濃度差之方式，將氫供體供應給該脫氮槽Γ 並且，在所述脫氮處理方法中，較佳的是，以該水力 學的停留時間中脫氮槽内氫供體的最大濃度與最小濃度的 差爲麻gTOK方式，將氫供體供應給該脫氣槽。 上亚且’在所述脫氣處理方法中，較佳的S,該水力學 的分留b間中脫氮槽内氫供體的最小濃度是最大濃度的 1/2以下。 二 在所述脫氮處理方法中，較佳的是，將氫供體 間歇地供應給該脫氮槽。 並且，在所述脫氮處理方法中，較佳的是，相對於硝 酸=子、亞硝酸離子的濃度，以脫氮處理所需要的氫供體 的供應量爲基準，組合將少於所述基準值量的氫供體供應 給該脫氮槽的第—供應程序、以及將多於所述基準值量的 氧七、體供應給5亥脫氮槽的第二供應程序，將氫供體供應給 該脫氮槽。 心 並且，在所述脫氮處理方法中，較位的是，氫供體的 仏應彳τ止時間比氫供體的供應時間的5〇0/。更長。 並且，在所述脫氮處理方法中，較传的是，該第一供 6 201002629 =:=Γ比所述第二供應程序中的氫供 並且，在所述脫氮處理方法中，較佳的是，在多次進 仃風供體的供應以及停止循環的情况下，_次循環的時間 比該水力學停留時間的50%更短。 …並且，在所述脫氮處理方法中，較佳的是，在多次進 仃该第-供應程序以及該第二供應程序循環的情况下，一 次循環時間比該水力學停留時間的50%更短。 並且，在所述脫氮處理方法中，較佳的是，所述水力 學停留時f种脫氮槽内氫供體的最小濃度在⑽mgTOC/L 以下。 並且’在所述魏處财法巾，較佳的是，該氯供體 從甲醇、乙醇、異两醇、酷酸、氯氣、丙酉同、葡萄糖、甲 乙酮中選擇。 "並且’本發明是脫氮處理裝置，包括完全混合型的脱 氮槽、將被處理水連續供應給該脫氮槽的被處理水供應裝 置、以及將風供體供應給該脱氮槽的氨供體供應裝置，並 且在該脫氮槽内，透過脫氮菌將被處理水中含有的峭醆離 子、亞硝酸離子還原成氮；其甲，該氫供體供應裝置，以 所述脫氮槽内被處理水的水力學停留時間中脫氮槽内氫供 體的濃度隨時間變化之方式，並且以該水力學停留時間中 脫氮槽内氫供體的最大濃度與最小濃度的差成爲誘導該脫 氮菌自己造粒化的濃度差之方式’將虱供體供應給該脫氮 槽。 201002629 發明的效果 根據本發明，能夠在將被處理水連續流入完全混合型 的脫氮槽，同時使脫氮菌顆粒化，能夠實現裝置的小型化 以及低成本化。 【實施方式】 以下，對本發明的實施方式進行說明。本實施方式是 實施本發明的一個實例，本發明並沒有被限定爲本實施方 式。 第一圖是顯示出了本實施方式相關的水處理裝置之概 略構成圖。如第一圖所示，水處理裝置1包括：氟處理裝 置10、硝化裝置12及脫氮裝置14。雖然本實施方式是關 於含有硝酸離子、亞硝酸離子之被處理水的脫氮處理方法 及脫氮處理裝置，但是，例如在半導體工廠排水等的電子 工業排水等中，大多作爲含氟及含有氨性氮排水排出，在 這種情况下，需要透過該氟處理裝置10去除氟，並透過硝 化裝置12將氨性氮硝化爲硝酸或亞硝酸。 氨性氮來自於氨、氨化合物、胺系化合物、例如四曱 基氫氧化敍、乙醇胺、其他胺酸等的有機性氮化合物。敦 來自於氫氟酸、氟化合物等。並且，關於氟處理裝置10的 構成及氟去除方法、硝化裝置12的構成及硝化方法，雖然 下面對其中一個實例進行說明，但裝置構成及方法並不僅 限於此。 氟處理裝置10包括：被處理水槽、反應槽及沉澱槽。 8 201002629 、反應槽的出口和沉澱 被處理水槽的出口和反應槽的入口 槽的入口透過管道連接。 硝化裝置12包括被處理水槽和硝化槽。氟處理穿置 沉澱槽的出口與硝化裝置12被處理水样的 、衣 J v 、石肖^{卜_ ^ 12被處理水槽的出口與頌化槽入口透過管道連接 第二圖是顯示出了本實施方式脫氤裝置構成之 圖。如第二圖所顯示，脫氮裝置14包括：脫氮槽Μ '，工 槽18、沉澱槽20、被處理水流入管22、污泥^還管虱化 處理水取出管26a、26b、26c、氫供體供應裝置^&及24 η 調整裝置30。被處理水流人管22是用於將被處理水供應13 脫亂槽16的流路。第一圖顯示出的確化裝置12確化槽 出口與第二圖顯示出的脫氮槽16被處理水供應口，透^ 處理水流入官22連接。脫氮槽16的處理水出口盥 18的入口，透過處理水取出管26a連接’氧化槽18、的出口曰 槽2〇的入口，透過處理水取出管26b連接，沉_ 的處理水出口與處理水取出管26c連接。沉殿槽2〇的、、一曰 ，排，口與脫氮槽丨6的污泥流入口，經由泵23,透過污= 达還官24連接。在脫氮槽16 β，設置有對槽内的水進匕 攪拌的攪拌裝置32。 丁 二氳供體供應裝置28，用於將氫供體供應至脫氮槽16 括：收錢供體的氫供體箱％、將氫供體送_氮抑 的泵36、組成氫供體的流路的氫供體流入管38、控制^ 36的驅動並控制氫供體的供應量的控制裝置4G。氫供體^ 的出口與脫氮槽16的氫供體供應口，經由泵％，透過 201002629 氫供體流入管38連接。泵36與控制裝置40電性連接。 pH調整裝置30，用於調整脫氮槽16内被處理水的 pH，並包括：pH調整劑箱42，用於收容鹽酸等酸或者氫 氧化鈉等鹹的pH調整劑；泵44，用於將pH調整劑送到脫 氮槽16 ; pH調整劑流入管46，組成pH調整劑的流路；pH 傳感器48，用於測定脫氮槽16内被處理水的pH值；以及 控制裝置50，用於控制泵44的驅動，並控制pH調整劑的 供應量。pH調整劑箱42的出口與脫氮槽16的pH調整劑 供應口，經由泵44，透過pH調整劑流入管46連接。pH 傳感器48與控制裝置50、控制裝置50與泵44電性連接。 接著，對本實施方式相關的水處理方法及水處理裝置1 的動作進行說明。首先，將含有氟及氨性氮的被處理水送 到第一圖顯示出的氟處理裝置10之被處理水槽。在該被處 理水槽中，在將被處理水的流量及濃度平均化，並調整pH 之後，將被處理水送到氟處理裝置10的反應槽。並且，將 鈣化合物供應到反應槽中。並且，在氟處理裝置10的反應 槽中，使被處理水中的氟與詞化合物反應，生成氟化約 (CaF2)。這裏，爲了提高被處理水中氟的處理效率，也可 以將凝聚劑與鈣化合物同時供應到氟處理裝置10的反應槽 中，使所述生成的氟化鈣聚集化。並且，在氟處理裝置10 的沉澱槽中，對含有（已聚集化的）氟化鈣的被處理水進 行固液分離，從被處理水中去除氟（以及氟化鈣）。 並且，氟處理裝置10也可以包括多個反應槽。例如， 也可以包括第一反應槽和第二反應槽，在第一反應槽，使 10 201002629 含有氟及氨性氮的處理水和鈣化合物反應，生成氟化鈣， 在第二反應槽’添加凝聚劑，使氟化鈣聚集化。並且，在 反應槽也可以設置對槽内的水進行攪拌的攪拌機構。 供應給氟處理裝置1〇反應槽的鈣化合物，並沒有被特 別限制爲能夠將氣作爲鼠化4弓析出的化合物，例如，氫氧 化鈣（Ca(OH)2)、氣化鈣（CaCl2)、硫酸鈣（CaS〇4)等都可以。 並且，作爲凝聚劑，可以使用例如多氣化銘或硫酸|呂等無 機凝聚劑或陰離子性聚合體等有機高分子凝聚劑等。 接著，將去除氟後的含有氨性氮的被處理水，送到第 一圖顯示出的硝化裝置12被處理水槽中。在該被處理水措 中，在將被處理水的流量及濃度平均化，並調整pH之後: 將被處理水送到硝化槽。在硝化槽中填充，透過使含有硝 化菌的微生物膜保持在載體上而形成微生物保持載體。並 且丄在硝化槽中，連接空氣導入管（未示出），形成能夠= 空氣供應到硝化槽内的被處理水中之構造。並且，在硝化 槽，透過微生物保持載體的硝化菌之作用，使被處理水中匕 的氨性氮硝化成硝酸性氮、亞硝酸性氮。這裏，硝化菌治 將被處理水中含有的氨性氮硝化成亞俩性氮之獨立^ 性=菌的氨氧化細菌、將亞硝酸性氮魏成硝酸性氮爵 立呂養性細菌的亞硝酸氧化細菌等。This is also true in wastewater treatment with nitrogen. For example, as the ammonia-containing nitrogen-containing wastewater treatment, after passing through ammonia-oxidizing bacteria, nitrite ions, and nitrate ions, 3 201002629, the nitrite ion and the nitrate ion are reduced to nitrogen by the denitrifying bacteria. In this case, as the hydrogen donor, the branched matter or the like contained in the drainage can be used. However, when the hydrogen donor is insufficient, it is necessary to supply it from the outside. Here, the hydrogen donor determines the supply amount based on the nitrogen concentration in the drainage, and continuously adds the hydrogen donor based on the supply amount. Among them, in the denitrification treatment in which the nitrite ion and the nitrate ion are reduced to nitrogen by the denitrifying bacteria, in addition to the activated sludge method, in order to increase the degree of denitrification bacteria and to facilitate solid-liquid separation, it is added or A method of performing a denitrification treatment using a gel-like carrier. Further, there is a method in which the denitrifying bacteria itself is granulated to form a block having a relatively high specific gravity, that is, a granule is formed, and the concentration of the denitrifying bacteria in the tank is remarkably increased to perform denitrification treatment. In the treatment method using the granulated denitrifying bacteria, in order to be able to maintain a high concentration of the denitrifying bacteria in the tank, the processing speed of the tank is faster than that of the method of adding the carrier. Cost reduction. In addition, since the specific gravity of the particles is high and the deposition speed is fast, it is easy to have solid-liquid separation. Such granule formation is countered by anaerobic decane fermentation, upflow sludge blanket reactor (XJSB) "sequencing batch reactor (SBR), ( For example, refer to Patent Documents 1 to 3). ~ Patent Document 1: Japanese Patent Laid-Open No. 63_258695, Philippe Philippe, Patent Document 2: Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. 1 262996. Patent Document: 3: Japanese Special Opening 2〇〇〇_51893 Mirror Public Pole [Invention] 4 201002629 The problem is that the degassing tank is completely mixed in the batch reactor. In a denitrification tank, the inflow of treated water, the supply of oxygen and the contact of the treated water with the denitrifying bacteria, and the denitrifying bacteria The four procedures of deposition and treatment of water discharge are processed. However, since the inflow of the treated water and the discharge of the treated water are all performed in a short time, the fluctuation of the treatment flow rate becomes large, and a large flow rate adjustment groove is required in the apparatus. Therefore, although it is an advantageous device for convenience in a small-scale device, it is difficult to apply to a medium-to-large-scale device. Further, in the case of using the upflow sludge layer reactor, although a very high treatment speed is obtained, the cost of the equipment is increased due to the use of a special shape denitrification tank. In addition, since the stirring of the inside of the denitration tank is not sufficiently performed in the configuration of the apparatus, it is difficult to control the pH of the water to be treated, and there is a problem that scale is generated and inorganic substances are accumulated in the particles in the water to be treated. . In order to solve such a problem, it is desirable to use a completely mixed type denitrification tank currently used in most apparatuses, and to construct a device in which the water to be treated continuously flows (and continuously discharges), but so far, there is no such thing as in the configuration of such a device. Denitrifying bacteria particle formation report. Therefore, in the denitrification treatment in which the nitrate ions and the nitrite ions contained in the water to be treated are reduced to nitrogen by the denitrifying bacteria, the water to be treated is continuously flowed into the completely mixed type denitrification tank. At the same time, the denitrifying bacteria are granulated. Technical Solution for Solving the Technical Problem 5 201002629 The denitrification treatment method of the present invention, the left full mixed Wei IUf, the bribe water is continuously supplied to the finished i, the donor, and the dehydrated bacteria will be treated by the denitrifying bacteria. , the reduction of the sub-stone _ sub-reduction into nitrogen, Μ, _ the hydrodynamics of the treated water in the denitrification tank 彳 毡 ... ... ... ... 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢The difference between the maximum concentration and the minimum concentration of the hydrogen donor in the water-nitrogen tank becomes a way to induce the difference in the granulation concentration of the bacterium, and the hydrogen donor is supplied to the denitrification tank, and in the denitrification treatment method, Preferably, the difference between the maximum concentration and the minimum concentration of the hydrogen donor in the denitrification tank in the residence time of the hydraulics is the gTOK mode, and the hydrogen donor is supplied to the degassing tank. In the above-described degassing treatment method, preferably S, the minimum concentration of the hydrogen donor in the denitrification tank in the hydrodynamic separation b is 1/2 or less of the maximum concentration. In the denitrification treatment method, it is preferred that a hydrogen donor is intermittently supplied to the denitrification tank. Further, in the denitrification treatment method, it is preferable that the combination is less than the concentration of the nitric acid and the nitrite ion, based on the supply amount of the hydrogen donor required for the denitrification treatment. a first supply procedure in which a reference amount of hydrogen donor is supplied to the denitrification tank, and a second supply procedure in which more than the reference amount of oxygen is supplied to the 5 Hade denitration tank, and the hydrogen donor is supplied Supply to the denitrification tank. In addition, in the denitrification treatment method, it is inferior that the hydrogen donor has a 仏 彳 止 time of less than 5 〇 0 / of the hydrogen donor supply time. Longer. Moreover, in the denitrification treatment method, it is further transmitted that the first supply 6 201002629 =:=Γ is more than the hydrogen supply in the second supply program, and in the denitrification treatment method, preferably In the case where the supply of the hurricane donor is repeated multiple times and the circulation is stopped, the time of the _ cycle is shorter than 50% of the hydraulic residence time. And, in the denitrification treatment method, preferably, in a case where the first supply step and the second supply program cycle are performed a plurality of times, one cycle time is 50% of the hydraulic residence time. Shorter. Further, in the denitrification treatment method, it is preferable that the minimum concentration of the hydrogen donor in the denitrification tank in the hydrodynamic residence is (10) mg TOC/L or less. Further, in the above-mentioned chemical method, it is preferred that the chlorine donor is selected from the group consisting of methanol, ethanol, isoamyl alcohol, sulphuric acid, chlorine gas, propylene carbonate, glucose, and methyl ethyl ketone. "and' the present invention is a denitrification treatment apparatus comprising a fully mixed type denitrification tank, a treated water supply device for continuously supplying treated water to the denitrification tank, and a wind donor to the denitrification tank An ammonia donor supply device, and in the nitrogen removal tank, the ruthenium ions and nitrite ions contained in the water to be treated are reduced to nitrogen through the denitrifying bacteria; and the hydrogen donor supply device is The manner in which the concentration of the hydrogen donor in the denitrification tank changes with time in the hydrodynamic residence time of the treated water in the nitrogen tank, and the difference between the maximum concentration and the minimum concentration of the hydrogen donor in the denitrification tank in the hydrodynamic residence time The method of inducing the difference in concentration of the denitrifying bacteria itself granulation is to supply the hydrazine donor to the denitrification tank. According to the present invention, it is possible to continuously flow the water to be treated into the denitration tank of the complete mixing type, and to granulate the denitrifying bacteria, thereby achieving downsizing and cost reduction of the apparatus. [Embodiment] Hereinafter, embodiments of the present invention will be described. This embodiment is an example for carrying out the invention, and the invention is not limited to the embodiment. The first figure is a schematic configuration diagram showing a water treatment apparatus according to the present embodiment. As shown in the first figure, the water treatment apparatus 1 includes a fluorine treatment unit 10, a nitrification unit 12, and a denitrification unit 14. In the present embodiment, the denitrification treatment method and the denitrification treatment apparatus for the water to be treated containing the nitrate ions and the nitrite ions are used, for example, in the electronic industrial drainage such as the semiconductor factory drainage, etc., and most of them are fluorine-containing and ammonia-containing. The nitrogen discharge is discharged, and in this case, it is necessary to remove fluorine through the fluorine treatment device 10, and to nitrate the ammonia nitrogen into nitric acid or nitrous acid through the nitrification device 12. The ammonia nitrogen is derived from ammonia, an ammonia compound, an amine compound, an organic nitrogen compound such as tetrakisyl hydroxide, ethanolamine or other amine acids. From the hydrofluoric acid, fluorine compounds. Further, the configuration of the fluorine treatment apparatus 10, the fluorine removal method, the configuration of the nitrification apparatus 12, and the nitrification method will be described below, but the apparatus configuration and method are not limited thereto. The fluorine treatment apparatus 10 includes a treated water tank, a reaction tank, and a sedimentation tank. 8 201002629, outlet and precipitation of the reaction tank The outlet of the treated water tank and the inlet of the reaction tank are connected through a pipe. The nitrification unit 12 includes a treated water tank and a nitrification tank. The outlet of the fluorine treatment through the sedimentation tank and the water treatment device of the nitrification unit 12, the outlet of the treatment tank, the outlet of the treated water tank and the inlet of the purification tank through the pipeline are shown in the second figure. A diagram of the configuration of the disengaging device of the present embodiment. As shown in the second figure, the denitrification device 14 includes: a nitrogen removal tank Μ ', a working tank 18, a sedimentation tank 20, a treated water inflow pipe 22, a sludge, and a deuterated treatment water removal pipe 26a, 26b, 26c, Hydrogen donor supply device ^& and 24 η adjustment device 30. The treated water flow pipe 22 is a flow path for the treatment water supply 13 to distort the tank 16. The first figure shows the confirmation device 12 confirming the outlet of the tank and the treated water supply port of the denitrification tank 16 shown in the second figure, and the treatment water inflow port 22 is connected. The inlet of the treated water outlet port 18 of the denitrification tank 16 is connected to the inlet of the outlet tank 2〇 of the oxidation tank 18 through the treated water take-out pipe 26a, and is connected to the treated water take-off pipe 26b, and the treated water outlet and treatment of the sink_ The water take-out tube 26c is connected. The sludge inlets of the slabs, the sump, the sump, and the denitrification tank 6 are connected via a pump 23 through the sewage. In the denitrification tank 16β, a stirring device 32 for agitating the water in the tank is provided. A DME supply device 28 for supplying a hydrogen donor to the denitrification tank 16 includes: a hydrogen donor tank % for collecting money donors, a pump 36 for sending hydrogen donors to nitrogen, and a hydrogen donor The hydrogen donor of the flow path flows into the tube 38, controls the drive of the control unit 36, and controls the supply amount of the hydrogen donor. The outlet of the hydrogen donor ^ and the hydrogen donor supply port of the denitrification tank 16 are connected to the hydrogen supply inflow pipe 38 through the 201002629 via the pump %. The pump 36 is electrically connected to the control device 40. The pH adjusting device 30 is configured to adjust the pH of the water to be treated in the denitrification tank 16, and includes a pH adjuster tank 42 for containing an acid such as hydrochloric acid or a salty pH adjusting agent such as sodium hydroxide; and a pump 44 for The pH adjuster is sent to the denitrification tank 16; the pH adjuster flows into the tube 46 to form a flow path of the pH adjuster; the pH sensor 48 is used to measure the pH of the treated water in the denitrification tank 16; and the control device 50, It is used to control the driving of the pump 44 and to control the supply amount of the pH adjuster. The outlet of the pH adjuster tank 42 and the pH adjuster supply port of the denitrification tank 16 are connected to the pH adjuster inflow pipe 46 via the pump 44. The pH sensor 48 is electrically connected to the control device 50, the control device 50, and the pump 44. Next, the water treatment method and the operation of the water treatment device 1 according to the present embodiment will be described. First, the water to be treated containing fluorine and ammonia nitrogen is sent to the treated water tank of the fluorine treatment apparatus 10 shown in the first figure. In the treated water tank, after the flow rate and concentration of the water to be treated are averaged and the pH is adjusted, the water to be treated is sent to the reaction tank of the fluorine treatment apparatus 10. Also, a calcium compound is supplied to the reaction tank. Further, in the reaction tank of the fluorine treatment apparatus 10, fluorine in the water to be treated is reacted with the word compound to form fluorinated (CaF2). Here, in order to improve the treatment efficiency of fluorine in the water to be treated, the coagulant and the calcium compound may be simultaneously supplied to the reaction tank of the fluorine treatment apparatus 10 to aggregate the calcium fluoride formed. Further, in the precipitation tank of the fluorine treatment apparatus 10, the water to be treated containing (aggregated) calcium fluoride is subjected to solid-liquid separation, and fluorine (and calcium fluoride) is removed from the water to be treated. Also, the fluorine treatment device 10 may include a plurality of reaction tanks. For example, a first reaction tank and a second reaction tank may be included. In the first reaction tank, 10 201002629 treated water containing fluorine and ammonia nitrogen is reacted with a calcium compound to form calcium fluoride, which is added in the second reaction tank. A coagulant that aggregates calcium fluoride. Further, a stirring mechanism for stirring the water in the tank may be provided in the reaction tank. The calcium compound supplied to the reaction vessel of the fluorine treatment apparatus is not particularly limited to a compound capable of causing gas to be precipitated as a rat, for example, calcium hydroxide (Ca(OH) 2 ) or calcium sulfide (CaCl 2 ). Calcium sulfate (CaS〇4) can be used. Further, as the aggregating agent, for example, an organic polymer flocculating agent such as an inorganic agglomerating agent such as polysulfide or sulfuric acid/lu or an anionic polymer can be used. Next, the treated water containing ammonia nitrogen after removing the fluorine is sent to the treated water tank of the nitrification apparatus 12 shown in the first figure. In the treated water method, after the flow rate and concentration of the water to be treated are averaged and the pH is adjusted: the treated water is sent to the nitrification tank. The microcapsule is filled in the nitrification tank, and the microbial retention carrier is formed by holding the microbial membrane containing the nitrifying bacteria on the carrier. Further, in the nitrification tank, an air introduction pipe (not shown) is connected to form a structure capable of supplying air to the water to be treated in the nitrification tank. Further, in the nitrification tank, the ammonia nitrogen of the ruthenium in the treated water is nitrated into nitric acid nitrogen and nitrite nitrogen by the action of the nitrifying bacteria which maintain the carrier by the microorganism. Here, the treatment of nitrifying bacteria will nitrate the ammonia nitrogen contained in the treated water into an independent nitrogen of the two nitrogens = ammonia oxidizing bacteria of the bacteria, and nitrite oxidation of the nitrite nitrogen into the nitric nitrogen-nitrogen bacteria. Bacteria, etc.
保持硝化菌的載體，雖然沒有特別的限制，但 =列如海錦、凝朦、塑料成型品等。具體來 利用親水性的聚氨基甲酸酯料、聚乙_凝膠等。X 接著，將所述硝化處理後的硝化處理液，即含有_ 201002629 性氮、亞硝酸性氮的被處理水’透過被處理水流入管22送 到脫氮裝置14的脫氮槽16中。這裏，脫氮槽16是完全混 合型的脫氮槽I6，在脫氮處理時，將被處理水連續供鹿給 脫氮槽16。並且’使泵36工作，將氫供體供應裝置28氣 供體箱34内的氫供體透過氫供體流入管38供庫仏二 16。在脫刚内，在含有脱讓污泥浮游二= 下進行收容，透過該脫氮菌作用，被處理水中的硝酸離子、 亞硝酸離子被還原成氮氣。在使用曱醇作爲氫供體的情况 下，被處理水中的硝酸離子、亞硝酸離子透過下面反應式 中示出的反應被還原成氮氣。 2N〇2 + CH3OH — N2 + C02 + H2〇 + 20H - 6NO3 + 5CH3OH —> 3N2 + 5C02 + 7H2O + 60H- 接著，經由處理水取出管26a’將透過脫氮處理去除硝 酸離子、亞硝酸離子的處理水送到氧化槽18，並在氧化槽 18，使處理水中殘留的氫供體等有機物氧化。接著，經由 處理水取出管26b，將去除氫供體的處理水送到沉澱槽2〇。 並且，在沉澱槽20的下部，被處理水中含有（本實施例中 爲自己造粒化）脫氣菌作爲污泥堆積’將沉澱槽2〇上部的 上澄水從處理水取出管26c取出。並且，使果23工作，將 堆積在沉澱槽20下部的污泥從污泥送還管％再次送還到 脫氮槽16内。並且’在雜裝置12進行石肖化處理以浮游 式污泥進行的情况下’也可以將污泥送還到硝化槽。 第三圖是顯不出本發明其他實施方式關於脫氮裝置構 成-例的模式圖。在脫氮裝置14中，不必將沉殿槽2〇與 12 201002629 脫氮槽16獨立設置，如第三圖所示，也可以在脫氮槽16 内設置下部開口的間壁52，形成脫氮室54及沉澱室56。 並且，固液分離也可以不使用第二圖顯示出的沉澱槽20、 第三圖顯示出的沉澱室56，而是以氣固分離器（GSS )、膜 分離裝置等任意裝置進行。 氧化槽18，用於將被處理水中含有的氫供體等有機物 透過微生物的作用進行氧化分解。如第二圖所示，氧化槽 18也可以設置在沉澱槽20的上游侧，也可以設置在沉澱槽 20的下游側。 接著，對氫供體的供應方法進行詳細描述。通常，根 據供應到脫氮槽16被處理水的硝酸離子、亞硝酸離子的濃 度算出脫氮處理所需要的氫供體的供應量，並且不改變該 供應量而連續地供應給脫氮槽16。因此，脫氮槽16内的氫 供體的濃度大致穩定在低濃度。並且，爲了有效地進行脫 氮處理，將脫氮槽16内的硝酸離子以及亞硝酸離子的脫氮 處理所需要氫供體供應量的（需要的氳供體的理論量）1.2 倍左右供應給脫氮槽16。 但是，在本實施方式中，脫氮槽16内被處理水之水力 學的停留時間（HRT)中，脫氮槽16内的氫供體的濃度隨 時間變化，該水力學的停留時間中脫氮槽16内氫供體的最 大濃度與最小濃度的差，成爲誘導脫氮菌的自己造粒化（顆 粒化）的濃度差，並以該方式將氫供體供應給脫氮槽16。 具體而言，在控制裝置40，預先記錄水力學的停留時間中 脫氮槽16内氫供體的濃度變動圖，基於濃度變動圖，以氫 13 201002629 供體的最大濃度與隶小濃度的差，成爲誘導脫氮菌自己造 粒化濃度差的方式控制泵36的工作，並調節氫供體的供應 量。即，進行後述的氫供體的供應一停止、氫供體的多量 供應一少量供應。 這裏，較佳的是，脫氮槽16内被處理水之水力學的停 留時間中，脫氮槽16内氫供體的最大濃度與最小濃度的差 在50mgTOC/L以上，並以該方式將氫供體供應到脫氮槽 16内，更較佳的是’以濃度差在i〇〇mgTOC/L以上的方式 將氫供體供應到脫氮槽16内。當脫氮槽16内被處癦水之 水力學的停留時間中’脫氮槽16内氫供體的最大濃度與最 小濃度的差小於50mgTOC/L時，存在不能充分誘導腺氮菌 自己造粒化的情况。 這晨，車父"It的疋，脫鼠槽16内被處理水之水力學的停 留時間中，脫氮槽内氫供體的最小濃度在最大濃度的1/2 以下（大於0，小於等於最大濃度的1/2的範圍）。當所述 最小濃度超過最大濃度的1/2時，存在脫氮菌自己造粒化 的誘導變困難的情况。 在本貫施方式中，透過將氫供體間歇地供應給赋氮槽 心能夠使脫氮槽16内被處理水之水力學的停留時間中， 脫氮槽16内氫供體的濃度隨時間變化。即，由於在氮供體 的仏應時’此夠使脫氮槽16内氫供體的濃度增加，並且在 虱供體的供應停止時，能夠使脫氮槽16内氫供體的濃度减 )(由於透過脫氮處理氫供體被消耗），因此能夠使所述水 力子的4了召日守間中脫氮槽16内氮供體的濃度隨時間變化。 14 201002629 但疋’氢供體的供應及停止時間、氫供體的供應量必須被 設定成’脫虱槽16内被處理水之水力學的停留時間（HRT) 中脫氣才曰16内氫供體的最大濃度與最小濃度的差在例如 50mgTOC/L 以上。 車乂仫的疋，氫供體供應停止時間比氫供體供應時間的 50%更長。當氫供體供應停止時間在氫供體供應時間的5〇% 以下時，即使氫供體的最大濃度與最小濃度的差在例如 ,5GmgTQC7L以上’也會存在脫氮S自己造粒化的充分誘導 變困難的情况。 在氫供體的供應及停止的循環進行多次的情况下，較 仫的疋，一次循環（供應一停止）的時間比水力學的停留 日守間的50/。更短，即相對於水力學的停留時間進行兩次循 環=上。如果相對於水力學的停留時間僅進行一次循環， 則風供體的最大濃度與最小濃度的差變大，但是，由於氮 供體的濃度高的處理水向脫氮槽16外排出，因此在用於從 t 處理水去除氫供體氧化槽18的負载變高之同時，存在處理 半水質惡化的情况。並且，由於在脫氮處理中，沒有被有 效使，的氳供體變多，需要使氫供體供應量增加，因此存 在脫氮處理的成本變高的情况。 並且，在本實施方式中，相對於脫氮槽16内硝酸離子 及，石肖酸離子的滚度，以脫氮處理所需要氫供體的供應量 要的氫供體的理論量）爲基準’組合將少於基準值的 供體:應給脫氮槽16的第—供應程序、及將多於所 V ?々畺的氫供體供應給脫氮槽16的第二供應程序， 15 201002629 透過將氫供體供應給脫氮槽16，也能夠使脫氮槽i6内被處 理水之水力學的停留睹Φ，盼Λ· i ^ 、中脫虱才曰16内的氫供體的濃度 隨時間變化。但是’在第—供應程序以及第二供應程序供 應氫供體的時間、及在該時間内供應的供應量必須被設定 成，脫氮槽16内被處理水之水力學的停留時間⑽中， 脫氮槽内氫供體的最大濃度與最小濃度的差在例如 50mgTOC/L 以上。 杈佳的是，第-供應程序中氫供體的供應時間比第二 供應程序中氫供體的供應時間5Q%更長。當第—供應程序 中氫供體的供應時間在第二供應程序中氫供體的供應時間 50%以下時，即使氫供體的最大濃度與最小濃度的差在例 如50mgTOC/L以上，也會存在脫氮菌自己造粒化的充分 導變困難的情况。 ° 在第一供應程序及第二供應程序的循環進行多次的情 况下，杈佳的疋，一次循環（第一供應程序一第二供應程 序）的時間比水力學的停留時間50%更短，即相對於 學的停留時間進行兩次循環以上。如果相對於水力學的停 留時間僅進行一次循環，則氫供體的最大濃度與最小濃^ 的差變大，但是，由於氳供體濃度高的處理水向脫氮槽= 外排出，因此在用於從處理水去除氫供體的氧化槽18的負 載變高之同時，存在處理水水質惡化的情况。並且，由於 在脫氮處理中，沒有被有效使用的氫供體變多，因此需要 增加氮供體的供應罝’存在脫氮處理成本變高的情况。 並且，在本實施方式中，較佳的是，脫氮槽16内被處 16 201002629 理水之水力學的停留時間中，脫氮槽16内氫供體的最小濃 度在100mgTOC/L以下，更較佳的是’在10mgTOC/L至 100mgTOC/L的範圍。當氫供體最小濃度大於100mgT〇C/L 時，存在脫氮菌自己造粒化的充分誘導變困難的情况。並 且，當氫供體最小濃度小於10mgTOC/L時，在用於從處理 水中去除氫供體的氧化槽18的負載變高之同時，存在處理 水水質惡化的情况。 並且，在顆粒化脫氮菌時’存在添加部分金屬類而獲 得良好結果的情况。一般來說’將這些作爲顆粒化促進物 質，作爲離子類，例如#5離子、鐵離子，作爲化合物類， 例如粉煤灰、氧化鐵、碳酸鈣等。關於其中的離子類，較 佳的是，在脫氮處理整個期間或裝置的啓動期間，連續或 間歇地添加。並且’關於化合物類，較佳的是，在啓動時 與污泥的添加同時進行添加。 本實施方式中使用的氫供體，例如爲甲醇、乙醇、異 丙醇、醋酸、氫氣、丙酮、葡萄糖、曱乙酮等，但並不即 制於此，作爲氳供體，可以使用現有已知的全部。 蔹硝酸離子、亞硝酸離子向氮氣的還原反應，雖然由 於氫供體的種類而有些不同，但是任何一種都是，由於生 成硝酸離子、亞輕離子等克分子的氫氧化合物離子 浮上槽内的被處理水PH上升。-般來說，適合將脫氮 中被處理水的pH調整至8〜9的範圍。但是，在氫供體 的碳酸離子的濃度變高、並且担心被處理水中含有的句離 子等產生結垢的情况下，較佳的是，將浮上槽内的被處理 17 201002629 水pH調整至6〜7.5的範圍，更佳的是，調整至6.3〜7.0的 範圍。具體而言，透過pH調整裝置30的pH傳感器48檢 測被處理水的pH，基於檢測的pH，透過控制裝置50使泵 44工作，將pH調整劑從pH調整劑箱42供應給脫氮槽16, 來調節脫氮槽16内的被處理水的pH，使得脫氮槽16内的 被處理水pH在所述pH範圍。 如上所述，在將被處理水連續供應給完全混合型的脫 氮槽的同時，將氫供體供應給脫氮槽，使得脫氮槽内被處 理水之水力學的停留時間中，脫氮槽16内氫供體的濃度隨 時間變化，並且在水力學的停留時間中脫氮槽16内氫供體 的最大濃度與最小濃度的差成爲誘導脫氮菌自己造粒化 (顆粒化）的濃度差，較佳在例如5OmgTOC/L以上，從而 能夠使脫氮菌顆粒化。透過使脫氮菌顆粒化，由於能夠增 加脫氮槽内的微生物濃度（污泥濃度），能夠提高脫氮處理 的處理速度，並能夠使裝置小型化或者低成本化。 以下，列舉出實施例和比較例，雖然更具體更詳細地 對本發明進行說明，但是本發明並不限定在以下的實施例。 實施例1 在實施例1中，使用與第二圖顯示出相同的裝置，將 下面表一中顯示出水質的被處理水連續通水至脫氮槽。使 用曱醇作爲氫供體，以脫氮槽内的被處理水的HRT中甲醇 的最大濃度與最小濃度的差在50mgTOC/L以上的方式，將 該曱醇間歇地供應給脫氮槽。將氫供體的停止時間和供應 時間的比固定爲1 : 19，供應一停止的一次循環的時間爲 18 201002629 HRT的1/5，透過流入氮負載使循環時間變化。甲醇的添加 量，相對於處理氮量爲3kg甲醇/kg氮，在試驗開始時爲約 500mgMLSS/L ’進行脫氮的活性污泥供應給脫氮槽。並且’ 脫氮槽利用50L容量的存儲罐，有效容積為 40L。使用鹽 酸將被處理水的pH調整爲pH6.5。並且，將留在設置於脫 氮槽後段沉澱槽的污泥送還至脫氮槽。試驗進行26天。The carrier for retaining the nitrifying bacteria is not particularly limited, but is classified as a brocade, a gel, a plastic molded article, and the like. Specifically, a hydrophilic polyurethane material, a polyethylene gel or the like is used. X Next, the nitrification treatment liquid after the nitrification treatment, i.e., the treated water containing _ 201002629 nitrogen and nitrous acid nitrogen, is sent through the treated water inflow pipe 22 to the denitrification tank 16 of the denitrification device 14. Here, the denitrification tank 16 is a completely mixed type denitrification tank I6, and the treated water is continuously supplied to the denitrification tank 16 in the denitrification treatment. And the pump 36 is operated to pass the hydrogen donor in the gas supply tank 34 of the hydrogen donor supply unit 28 through the hydrogen donor inflow pipe 38 for storage. In the detachment, the storage is carried out under the condition that the decontamination sludge is floated, and the nitrate ions and nitrite ions in the water to be treated are reduced to nitrogen gas by the action of the denitrifying bacteria. In the case where decyl alcohol is used as the hydrogen donor, the nitrate ions and nitrite ions in the water to be treated are reduced to nitrogen by the reaction shown in the following reaction formula. 2N〇2 + CH3OH — N2 + C02 + H2〇+ 20H - 6NO3 + 5CH3OH —> 3N2 + 5C02 + 7H2O + 60H- Next, the nitrate ion and nitrite ions are removed by the denitrification treatment via the treated water take-off tube 26a' The treated water is sent to the oxidation tank 18, and in the oxidation tank 18, an organic substance such as a hydrogen donor remaining in the treated water is oxidized. Next, the treated water from which the hydrogen donor is removed is sent to the sedimentation tank 2 via the treated water take-out pipe 26b. Further, in the lower portion of the sedimentation tank 20, degassed bacteria (granulated in the present embodiment) are contained as sludge accumulation in the water to be treated, and the upper water in the upper portion of the sedimentation tank 2 is taken out from the treated water take-out pipe 26c. Then, the fruit 23 is operated, and the sludge deposited in the lower portion of the sedimentation tank 20 is returned to the denitrification tank 16 again from the sludge delivery pipe. Further, in the case where the miscellaneous apparatus 12 performs the shale processing to carry out the floating sludge, the sludge may be returned to the nitrification tank. The third drawing is a schematic view showing an example of the configuration of the denitrification apparatus according to another embodiment of the present invention. In the denitrification device 14, it is not necessary to separately set the sinking tank 2〇 and the 12 201002629 denitrification tank 16, as shown in the third figure, a lower opening partition 52 may be provided in the denitrification tank 16 to form a nitrogen removal tank. Room 54 and precipitation chamber 56. Further, the solid-liquid separation may be carried out by any means such as a gas-solid separator (GSS) or a membrane separation device, without using the precipitation tank 20 shown in the second drawing and the precipitation chamber 56 shown in the third drawing. The oxidation tank 18 is for oxidatively decomposing an organic substance such as a hydrogen donor contained in the water to be treated by the action of microorganisms. As shown in the second figure, the oxidation tank 18 may be provided on the upstream side of the sedimentation tank 20 or on the downstream side of the sedimentation tank 20. Next, a method of supplying a hydrogen donor will be described in detail. In general, the supply amount of the hydrogen donor required for the denitrification treatment is calculated based on the concentration of the nitrate ion and the nitrite ion supplied to the water to be treated in the denitrification tank 16, and is continuously supplied to the denitrification tank 16 without changing the supply amount. . Therefore, the concentration of the hydrogen donor in the denitrification tank 16 is substantially stabilized at a low concentration. Further, in order to carry out the denitrification treatment efficiently, the supply amount of the hydrogen donor (the required theoretical amount of the ruthenium donor) required for the denitrification treatment of the nitrate ions and the nitrite ions in the denitrification tank 16 is supplied to about 1.2 times. Denitrification tank 16. However, in the present embodiment, in the hydraulic retention time (HRT) of the treated water in the denitrification tank 16, the concentration of the hydrogen donor in the denitrification tank 16 changes with time, and the hydraulic residence time is off. The difference between the maximum concentration and the minimum concentration of the hydrogen donor in the nitrogen tank 16 becomes a concentration difference of the self-granulation (granulation) of the induced denitrification bacteria, and the hydrogen donor is supplied to the denitrification tank 16 in this manner. Specifically, in the control device 40, the concentration variation map of the hydrogen donor in the denitrification tank 16 in the residence time of the hydraulics is recorded in advance, and the difference between the maximum concentration and the small concentration of the donor of hydrogen 13 201002629 is based on the concentration variation map. The operation of the pump 36 is controlled in such a manner as to induce the difference in the granulation concentration of the denitrifying bacteria, and the supply amount of the hydrogen donor is adjusted. That is, the supply of the hydrogen donor described later is stopped, and the supply of the hydrogen donor is supplied in a small amount. Here, it is preferable that the difference between the maximum concentration and the minimum concentration of the hydrogen donor in the denitrification tank 16 is 50 mg TOC/L or more in the residence time of the hydraulics of the treated water in the denitrification tank 16, and in this manner The hydrogen donor is supplied into the denitrification tank 16, and it is more preferable to supply the hydrogen donor to the denitrification tank 16 in such a manner that the difference in concentration is above i〇〇mgTOC/L. When the difference between the maximum concentration and the minimum concentration of the hydrogen donor in the denitrification tank 16 is less than 50 mg TOC/L in the residence time of the hydrodynamics of the dehydration tank in the denitrification tank 16, there is a possibility that the gland nitrogen bacteria cannot be sufficiently induced to granulate. Situation. In the morning, the father of the car "It, in the residence time of the hydrodynamics of the treated water in the derateration tank 16, the minimum concentration of the hydrogen donor in the denitrification tank is below 1/2 of the maximum concentration (greater than 0, less than A range equal to 1/2 of the maximum concentration). When the minimum concentration exceeds 1/2 of the maximum concentration, there is a case where the induction of granulation by the denitrifying bacteria becomes difficult. In the present embodiment, the concentration of the hydrogen donor in the denitrification tank 16 over time in the residence time of the hydrolyzed water in the denitrification tank 16 by intermittently supplying the hydrogen donor to the nitrogen-carrying tank core Variety. That is, since the concentration of the hydrogen donor in the denitrification tank 16 is increased when the nitrogen donor is supplied, and the supply of the rhodium donor is stopped, the concentration of the hydrogen donor in the denitrification tank 16 can be reduced. (Because the hydrogen donor is consumed by the denitrification treatment), the concentration of the nitrogen donor in the denitrification tank 16 in the desulfurization tank 16 can be changed with time. 14 201002629 However, the supply and stop time of hydrogen donors and the supply of hydrogen donors must be set to 'hydrogenation in the hydrodynamic residence time (HRT) of the treated water in the decanting tank 16 The difference between the maximum concentration and the minimum concentration of the donor is, for example, 50 mg TOC/L or more. In the rut of the rut, the hydrogen donor supply stop time is longer than 50% of the hydrogen donor supply time. When the hydrogen donor supply stop time is less than 5% of the hydrogen donor supply time, even if the difference between the maximum concentration and the minimum concentration of the hydrogen donor is, for example, 5 GmgTQC7L or more, the denitrification S itself may be sufficiently granulated. The situation in which the induction becomes difficult. In the case where the supply and stop cycles of the hydrogen donor are performed multiple times, the time of one cycle (supply-stop) is 50% longer than the time of the hydraulic stay. Shorter, that is, two cycles = upper relative to the residence time of the hydraulics. If only one cycle is performed with respect to the residence time of the hydraulics, the difference between the maximum concentration and the minimum concentration of the wind donor becomes large, but since the treated water having a high concentration of the nitrogen donor is discharged to the outside of the denitrification tank 16, The load for removing the hydrogen donor oxidation tank 18 from the t-treated water becomes high, and there is a case where the treatment half-water quality is deteriorated. Further, since the amount of the ruthenium donor is not effectively increased during the denitrification treatment, it is necessary to increase the supply amount of the hydrogen donor, and thus the cost of the denitrification treatment may become high. Further, in the present embodiment, the nitration of the nitrate ions and the succinic acid ions in the denitrification tank 16 is based on the theoretical amount of the hydrogen donor required for the supply amount of the hydrogen donor required for the denitrification treatment. 'Combination will be less than the reference value of the donor: the first supply procedure for the denitrification tank 16, and the second supply procedure for supplying more than the V?? hydrogen donor to the denitrification tank 16, 15 201002629 By supplying the hydrogen donor to the denitrification tank 16, the hydrodynamic retention of the treated water in the denitrification tank i6 can be made Φ, the concentration of the hydrogen donor in the 虱 i i ^ , middle 虱 虱 16 Change with time. However, the time during which the hydrogen supply is supplied to the first supply program and the second supply program, and the supply amount supplied during the time must be set to the residence time (10) of the hydraulics of the treated water in the nitrogen removal tank 16 The difference between the maximum concentration and the minimum concentration of the hydrogen donor in the denitrification tank is, for example, 50 mg TOC/L or more. Preferably, the supply time of the hydrogen donor in the first supply procedure is longer than the supply time of the hydrogen donor in the second supply procedure by 5Q%. When the supply time of the hydrogen donor in the first supply procedure is less than 50% of the supply time of the hydrogen donor in the second supply procedure, even if the difference between the maximum concentration and the minimum concentration of the hydrogen donor is, for example, 50 mg TOC/L or more, There is a case where it is difficult to sufficiently conduct the granulation of the denitrifying bacteria. ° In the case where the cycle of the first supply procedure and the second supply procedure is performed multiple times, the time of one cycle (first supply procedure and second supply procedure) is shorter than the residence time of hydraulics by 50%. , that is, two cycles or more with respect to the residence time of the study. If only one cycle is performed with respect to the residence time of the hydraulics, the difference between the maximum concentration of the hydrogen donor and the minimum concentration becomes large, but since the treated water having a high concentration of the donor is discharged to the denitrification tank, The load of the oxidation tank 18 for removing the hydrogen donor from the treated water becomes high, and the treated water quality deteriorates. Further, since the hydrogen donor which is not effectively used in the denitrification treatment is increased, it is necessary to increase the supply of the nitrogen donor, and the cost of the denitrification treatment is increased. Further, in the present embodiment, it is preferable that the minimum concentration of the hydrogen donor in the denitrification tank 16 is less than 100 mg TOC/L in the residence time of the hydrodynamics of the water removal tank 16 in the denitrification tank 16. Preferably, it is in the range of 10 mg TOC/L to 100 mg TOC/L. When the minimum concentration of the hydrogen donor is more than 100 mg T 〇 C / L, it is difficult to sufficiently induce the granulation of the denitrifying bacteria itself. Further, when the minimum concentration of the hydrogen donor is less than 10 mg TOC/L, the load of the oxidation tank 18 for removing the hydrogen donor from the treated water becomes high, and the treated water quality deteriorates. Further, in the case of granulated denitrifying bacteria, there is a case where a part of the metal is added to obtain a good result. Generally, these are used as granulating promoting substances, and as ionics, for example, #5 ions and iron ions, and compounds such as fly ash, iron oxide, calcium carbonate, and the like. With regard to the ionic species therein, it is preferred to continuously or intermittently add during the entire denitrification treatment or during the startup of the apparatus. Further, it is preferable that the compound is added at the same time as the addition of the sludge at the time of starting. The hydrogen donor used in the present embodiment is, for example, methanol, ethanol, isopropanol, acetic acid, hydrogen, acetone, glucose, acetophenone or the like, but it is not limited thereto. As the ruthenium donor, the existing one can be used. Know all. The reduction reaction of cerium nitrate ions and nitrite ions to nitrogen gas is somewhat different depending on the type of hydrogen donor, but any one of them is formed by the formation of hydroxide ions such as nitrate ions and sub-light ions in the tank. The treated water PH rises. In general, it is suitable to adjust the pH of the water to be treated in the denitrification to a range of 8 to 9. However, in the case where the concentration of carbonate ions in the hydrogen donor is high and there is a fear that scale is generated in the sentence ions or the like contained in the treated water, it is preferable to adjust the pH of the treated 17 201002629 water in the floating tank to 6 The range of ~7.5, and even better, is adjusted to the range of 6.3 to 7.0. Specifically, the pH of the water to be treated is detected by the pH sensor 48 of the pH adjusting device 30, and the pump 44 is operated by the control device 50 based on the detected pH, and the pH adjusting agent is supplied from the pH adjuster tank 42 to the denitrification tank 16 The pH of the water to be treated in the denitrification tank 16 is adjusted so that the pH of the water to be treated in the denitrification tank 16 is in the pH range. As described above, while the water to be treated is continuously supplied to the denitration tank of the complete mixing type, the hydrogen donor is supplied to the denitrification tank, so that the residence time of the hydrodynamics of the treated water in the denitrification tank is denitrified. The concentration of the hydrogen donor in the tank 16 varies with time, and the difference between the maximum concentration and the minimum concentration of the hydrogen donor in the denitrification tank 16 during the residence time of the hydraulics becomes the granulation (granulation) of the induced denitrifying bacteria. The difference in concentration is preferably, for example, at least 50 mg TOC/L, so that the denitrifying bacteria can be pelletized. By granulating the denitrifying bacteria, the microorganism concentration (sludge concentration) in the denitrification tank can be increased, the treatment speed of the denitrification treatment can be increased, and the apparatus can be downsized or reduced in cost. Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. [Example 1] In Example 1, the treated water showing the water quality in Table 1 below was continuously passed to the denitrification tank using the same apparatus as that shown in the second figure. Using decyl alcohol as a hydrogen donor, the decyl alcohol is intermittently supplied to the denitrification tank so that the difference between the maximum concentration of methanol and the minimum concentration in the HRT of the water to be treated in the denitrification tank is 50 mg TOC/L or more. The ratio of the stop time of the hydrogen donor to the supply time is fixed at 1:19, and the time for one cycle of supply to stop is 18/5 of the 020602629 HRT, and the cycle time is varied by the inflow of nitrogen load. The amount of methanol added was 3 kg of methanol/kg of nitrogen relative to the amount of nitrogen treated, and about 5 mg of MLSS/L' of activated sludge was supplied to the denitrification tank at the start of the test. And the denitrification tank uses a 50 L capacity storage tank with an effective volume of 40 L. The pH of the treated water was adjusted to pH 6.5 using hydrochloric acid. Further, the sludge remaining in the sedimentation tank in the latter stage of the denitrification tank is returned to the denitrification tank. The test was carried out for 26 days.
表一 硝酸鈉 500msN 氣化妈 〜_ 300mgCa 磷酸 10meP/L 自來水 1L 比較例 在比較例中’使用曱醇作爲氫供體，並將該曱醇連續 供應給脫氮槽。將脫氮槽内被處理水的HRT中甲醇的最大 濃度與最小濃度的差維持在不到5〇mgT〇C/L。甲醇的添加 量’相對於處理氮量爲3kg甲醇/kg氮，在試驗開始時爲約 500mgMLSS/L，進行脫氮的活性污泥供應給脫氣槽。並且， 脫氮槽利用50L容量的存儲罐，有效容積爲40L。使用鹽 酸將被處理水的pH調整爲ΡΗ6·5。並且，將留在設置於脫 氣槽後段的沉殿槽的污泥送還至脫氮槽。試驗進行26天。 第四圖是顯示出實施例1的試驗中MLSS濃度相對於 經過天數變化的圖。第五圖是顯示出實施例1的試驗中脫 氮處理的處理速度相對於經過天數變化的圖。如第四圖所 示’在實施例1中，在天數經過的同時，MLSS濃度上升， 從試驗開始在第26天，MLSS濃度達到8000mgMLSS/L。 19 201002629 並且，如第五圖所示，在MLSS濃度上升的同時，脫氮處 理的處理速度也上升，從試驗開始在第26天，達到約 2kgN/m3/天，並確認獲得較高的處理速度。並且，在實施 例1中，實驗開始至經過約2周後，確認含有脫氮菌的污 泥顆粒化；約3周後，確認含有脫氮菌的污泥大致全部顆 粒化。另一方面，在比較例中，從試驗開始在第26天， MLSS濃度僅達到3000mgMLSS/L，脫氮處理的處理速度也 爲0.6kgN/m3/天。此外，即使從試驗開始經過26天，含有 脫氮菌的污泥也沒有顆粒化。 實施例2 在實施例2中，除了將氫供體的停止時間/供應時間設 爲0.5、1、5、10、20、50之外，以與實施例1相同的條 件進行脫氮處理。並且，從試驗開始25天後，以下述的基 準評價脫氮槽内含有脫氮菌的污泥是否顆粒化，將其歸納 在表二中。 〇含有脫氮菌的污泥全部顆粒化 △含有脫氮菌的污泥一部分顆粒化 X含有脫氮菌的污泥沒有顆粒化 20 201002629 表二Table 1 Sodium nitrate 500msN Gasification mother ~_300mgCa Phosphoric acid 10meP/L Tap water 1L Comparative Example In the comparative example, decyl alcohol was used as a hydrogen donor, and the sterol was continuously supplied to the denitrification tank. The difference between the maximum concentration and the minimum concentration of methanol in the HRT of the treated water in the denitrification tank was maintained at less than 5 〇 mg T 〇 C / L. The amount of methanol added was 3 kg of methanol/kg of nitrogen relative to the amount of nitrogen to be treated, and was about 500 mg of MLSS/L at the start of the test, and the activated sludge for denitrification was supplied to the degassing tank. Further, the denitrification tank uses a 50 L capacity storage tank and has an effective volume of 40 L. The pH of the treated water was adjusted to ΡΗ6·5 using hydrochloric acid. Further, the sludge remaining in the sinking tank provided in the rear stage of the degassing tank is returned to the denitrification tank. The test was carried out for 26 days. The fourth graph is a graph showing the change in the MLSS concentration with respect to the number of days passed in the test of Example 1. Fig. 5 is a graph showing the change in the treatment speed of the denitrification treatment in the test of Example 1 with respect to the number of days passed. As shown in the fourth figure, in Example 1, the MLSS concentration increased while the number of days passed, and the MLSS concentration reached 8000 mg MLSS/L on the 26th day from the start of the test. 19 201002629 Moreover, as shown in the fifth figure, the treatment speed of the denitrification treatment also increases while the concentration of the MLSS rises, and reaches about 2 kgN/m3/day on the 26th day from the start of the test, and it is confirmed that a higher treatment is obtained. speed. Further, in Example 1, after about two weeks from the start of the experiment, it was confirmed that the sludge containing the denitrifying bacteria was pelletized; after about three weeks, it was confirmed that substantially all of the sludge containing the denitrifying bacteria was granulated. On the other hand, in the comparative example, on the 26th day from the start of the test, the MLSS concentration was only 3000 mg MLSS/L, and the treatment rate of the denitrification treatment was also 0.6 kg N/m 3 /day. Further, even after 26 days from the start of the test, the sludge containing the denitrifying bacteria was not pelletized. [Example 2] In Example 2, the denitrification treatment was carried out under the same conditions as in Example 1 except that the stop time/supply time of the hydrogen donor was set to 0.5, 1, 5, 10, 20, 50. Further, 25 days after the start of the test, whether or not the sludge containing the denitrifying bacteria in the denitrification tank was granulated by the following criteria was summarized in Table 2.污泥 All sludge containing denitrifying bacteria is granulated △ Part of the sludge containing denitrifying bacteria is pelletized X Sludge containing denitrifying bacteria is not pelletized 20 201002629 Table 2
從表二可以判、-i —-^ 比較例）的情况下 在彳〒止時間/添加時間爲〇 (所述 沒有顆粒化。並且，=使從試驗開始經過25天，脫氮菌也 試驗開始經過25 /田 '止時間/添加時間在1以上時，從 得良好的結果。天後，含有脫氮菌的污泥全部顆粒化，獲 實施例3 在實施例3中，除Ύ 設爲ΗΡτ从 X將供應一停止的一次循環的時間 n 的 1、1/2、v 脫氮處理。將供應 的氫供體平均濃度、 條件進弁1/5之外，以與實施例1相同的 史订脫氮處理。將佴廄 出D 66 供應〜停止的各循環時間内脫氮槽 脫氮槽出口的硝酸性氮平均濃度 %納在表 表三 中From the case of Table 2, it can be judged, -i - -^ Comparative Example), the time of the stop/addition time is 〇 (the above is not granulated. And, = 25 days after the start of the test, the denitrifying bacteria are also tested. When the 25/Ten's stop time/addition time was 1 or more, the results were good. After the day, the sludge containing the denitrifying bacteria was completely granulated, and Example 3 was obtained. In Example 3, the Ύ was set to ΗΡτ is supplied from X to the denitrification treatment of 1, 1/2, v of the time n of one cycle of the stop. The average hydrogen concentration and the condition of the supplied hydrogen donor are 1/5, which is the same as in the first embodiment. According to the history of denitrification treatment, the average concentration of nitrate nitrogen in the denitrification tank outlet of the denitrification tank in each cycle of the D 66 supply is stopped.
21 201002629 &在循環時間在HRT的丨/3以下的情况下，供應到脫氮 ^氫ί、體也被有效使用，處理水中的硝酸性氮也能夠抑制 爲幸乂低但疋，在循環時間在HRT的1/2以上的情况下， /】、、加的氫供體的—部分未反應而流出，與此相伴，確認氯 供體不足，處理水質惡化。 【圖式簡單說明】 第圖疋顯不出本實施方式相關水處理裝置一例的概略 構成圖。 第-圖是顯示出本實施方式相關脫氮裝置—例構成的模 式圖。 第三圖是顯示出本發明其他實施方式㈣脫氮裝置構成 一例的模式圖。 冲圖疋顯不出實施例1，與試驗經過天數相對應MLSS >辰度變化的圖。 ―圖疋顯不出貫施例i，與試驗經過天數相對應脫氮處 理之處理速度變化的圖。 【主要 1 10 12 14 16 元件符號說明】 水處理袭置 敦處理震置 確化褒置 脫氮裝置 脫氮槽 22 201002629 18 20 22 23 、 36 、 44 24 26a、26b、26c 28 30 32 34 38 40、50 42 46 48 52 54 56 氧化槽 沉澱槽 被處理水流入管 泵 污泥送還管 處理水取出管 氳供體供應裝置 pH調整裝置 攪拌裝置 氳供體箱 氫供體流入管 控制裝置 pH調整劑箱 pH調整劑流入管 pH傳感器 間壁 脫氮室 沉澱室 2321 201002629 & When the cycle time is below 丨/3 of HRT, the supply to denitrification and hydrogen is effective, and the nitrate nitrogen in the treated water can also be suppressed to be low but 疋, in circulation When the time is 1/2 or more of HRT, the part of the hydrogen donor is not reacted and flows out, and it is confirmed that the chlorine donor is insufficient and the treated water quality is deteriorated. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic block diagram showing an example of a water treatment apparatus according to the present embodiment. Fig. 1 is a schematic view showing a configuration of a denitrification apparatus according to the present embodiment. Fig. 3 is a schematic view showing an example of a configuration of a denitrification apparatus according to another embodiment (4) of the present invention. The graph of the MLSS > Chen degree change corresponding to the number of days after the test is not shown in the plan. The graph shows the change in the processing speed of the denitrification treatment corresponding to the number of days after the test. [Main 1 10 12 14 16 Description of component symbols] Water treatment and treatment of the denitrification tank of the denitrification unit 22 201002629 18 20 22 23 , 36 , 44 24 26a , 26b , 26c 28 30 32 34 38 40 50 42 46 48 52 54 56 Oxidation tank sedimentation tank treated water inflow pipe pump sludge return pipe treatment water removal pipe 氲 donor supply device pH adjustment device stirring device 氲 donor tank hydrogen donor inflow pipe control device pH adjuster tank pH adjuster inflow pipe pH sensor partition wall denitrification chamber precipitation chamber 23