TWI588097B - Method for treating fluoride containing waste water - Google Patents
Method for treating fluoride containing waste water Download PDFInfo
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Description
本發明是有關於一種廢水處理方法，且特別是有關於一種含氟廢水處理方法。 The present invention relates to a wastewater treatment method, and more particularly to a fluorine-containing wastewater treatment method.
隨著生活水準及工業化程度提高，在消費性電子產業、高科技產業、半導體產業及電子產業的迅速發展之下，相對地也提升了台灣的經濟發展，而也伴隨環境的汙染。 With the improvement of living standards and industrialization, under the rapid development of the consumer electronics industry, high-tech industry, semiconductor industry and electronics industry, Taiwan's economic development has also been relatively enhanced, accompanied by environmental pollution.
在上述產業中，氟系廢水是半導體產業主要的廢水排放之一。而廢水的主要來源例如為，晶圓清洗及濕蝕刻時使用氫氟酸後所產生的廢水，或者，回收水系統中再生樹脂後所產生之廢水，再或者，機台端局部廢氣處理設施(Local Scrubber)與中央廢氣洗滌塔(Center Scrubber)所排放之廢水。在巴塞爾公約中，將含氟廢水與汙泥歸類為有害廢棄物，必須在境內妥善處理並不得運送出境。如此可見，含氟廢水處理方法與技術研究係為環保領域的重要課題。 Among the above industries, fluorine-based wastewater is one of the major wastewater discharges in the semiconductor industry. The main sources of waste water are, for example, waste water produced by using hydrofluoric acid during wafer cleaning and wet etching, or waste water produced by recycling recycled resin in a water system, or a local exhaust gas treatment facility at the machine end (Local Scrubber) and wastewater discharged from the Center Scrubber. In the Basel Convention, fluorine-containing wastewater and sludge are classified as hazardous waste and must be disposed of properly in the country and must not be transported out of the country. It can be seen that the fluorine-containing wastewater treatment method and technology research department is an important issue in the field of environmental protection.
本發明提供一種含氟廢水處理方法，其能得出高純度的冰晶石結晶體，藉以提升回收價值。 The invention provides a fluorine-containing wastewater treatment method, which can obtain a high-purity cryolite crystal body, thereby improving the recovery value.
本發明提出一種含氟廢水處理方法，包括以下步驟。執行一進水步驟至一調勻槽，其中一待處理水以批次式操作進入至調勻槽，調勻槽內的待處理水包含一高濃度含氟廢水與一低濃度含氟廢水。藉由一氟離子偵測單元以控制調勻槽內之待處理水之氟離子濃度，其中當待處理水之氟離子濃度至一預定濃度時，停止供高濃度含氟廢水進入至調勻槽，當待處理水的水位達一預定液位時，停止供低濃度含氟廢水進入至調勻槽。導入待處理水與一鋁鹽溶液至一流體化床結晶槽，混合而得到一冰晶石結晶體。 The invention provides a method for treating fluorine-containing wastewater, comprising the following steps. A water inflow step is performed to a mixing tank, wherein a water to be treated enters the mixing tank in a batch operation, and the water to be treated in the mixing tank contains a high concentration fluorine-containing wastewater and a low concentration fluorine-containing wastewater. The fluorine ion detecting unit controls the fluoride ion concentration of the water to be treated in the mixing tank, wherein when the fluoride ion concentration of the water to be treated reaches a predetermined concentration, the high-concentration fluorine-containing wastewater is stopped from entering the mixing tank. When the water level of the water to be treated reaches a predetermined liquid level, the low-concentration fluorine-containing wastewater is stopped from entering the mixing tank. The water to be treated and an aluminum salt solution are introduced into a fluidized bed crystallization tank and mixed to obtain a cryolite crystal.
在本發明之一實施例中，流體化床結晶槽中的鋁與氟的比例在0.8：6至1.2：6的範圍間。 In one embodiment of the invention, the ratio of aluminum to fluorine in the fluidized bed crystallization tank is between 0.8:6 and 1.2:6.
在本發明之一實施例中，氟離子偵測單元包括一氟離子選擇電極與一氟離子偵測槽。於藉由氟離子偵測單元以控制調勻槽內之待處理水之氟離子濃度的步驟中，更包括以下步驟。導入高濃度含氟廢水及一離子液至氟離子偵測槽。接著，藉由氟離子選擇電極以檢測氟離子偵測槽中的氟離子濃度。 In an embodiment of the invention, the fluoride ion detecting unit comprises a fluoride ion selective electrode and a fluorine ion detecting groove. In the step of controlling the fluoride ion concentration of the water to be treated in the mixing tank by the fluorine ion detecting unit, the following steps are further included. Introduce high concentration fluorine-containing wastewater and an ionic liquid to the fluoride ion detection tank. Next, the fluorine ion selective electrode is used to detect the fluoride ion concentration in the fluoride ion detecting bath.
在本發明之一實施例中，於導入待處理水與鋁鹽溶液至流體化床結晶槽，混合而得到冰晶石結晶體的步驟中，更包括以下步驟。進行一分離步驟，以得到低濃度含氟廢水與一汙泥。接著，藉由氟離子偵測單元控制一回流幫浦，以將低濃度含氟廢水導入至調勻槽。 In an embodiment of the present invention, in the step of introducing the water to be treated and the aluminum salt solution to the fluidized bed crystallization tank and mixing to obtain the cryolite crystal, the following steps are further included. A separation step is performed to obtain a low concentration fluorine-containing wastewater and a sludge. Next, a reflux pump is controlled by the fluoride ion detecting unit to introduce the low concentration fluorine-containing wastewater into the mixing tank.
在本發明之一實施例中，於導入待處理水與鋁鹽溶液至流體化床結晶槽，混合而得到冰晶石結晶體的步驟中，更包括以下步驟。藉由一pH控制器以控制流體化床結晶槽內的pH值達到一預定pH值。接著，當流 體化床結晶槽內的pH值未在預定pH值的範圍內時，導入一鹼液以使流體化床結晶槽內的pH值達到預定pH值。 In an embodiment of the present invention, in the step of introducing the water to be treated and the aluminum salt solution to the fluidized bed crystallization tank and mixing to obtain the cryolite crystal, the following steps are further included. A pH controller is used to control the pH in the fluidized bed crystallization tank to a predetermined pH. Then, when the flow When the pH in the crystallization tank of the bed is not within a predetermined pH range, an alkali solution is introduced to bring the pH in the fluidized bed crystallization tank to a predetermined pH.
在本發明之一實施例中，預定pH值的範圍在5.0~5.5之間。 In one embodiment of the invention, the predetermined pH range is between 5.0 and 5.5.
基於上述，本發明之含氟廢水處理方法，使待處理水係以批次式而非連續式的方式進入調勻槽，可避免因進水水質變化過大而造成後續結晶效能不佳。再者，藉由上述氟離子偵測單元控制氟離子濃度在一定的範圍內，以維持在適合冰晶石結晶體的條件下，而得到高純度的冰晶石結晶體。 Based on the above, the fluorine-containing wastewater treatment method of the present invention allows the water to be treated to enter the mixing tank in a batch type rather than a continuous manner, thereby avoiding the subsequent crystallization failure due to excessive change of the influent water quality. Further, the fluoride ion detecting unit controls the fluorine ion concentration within a certain range to maintain the cryolite crystal in a high-purity cryolite crystal.
為讓本發明之上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。 The above described features and advantages of the present invention will be more apparent from the following description.
20‧‧‧調勻槽 20‧‧‧Regulation tank
22‧‧‧液位計 22‧‧‧Level gauge
24‧‧‧幫浦 24‧‧‧ pump
30‧‧‧氟離子偵測單元 30‧‧‧Fluoride detection unit
32‧‧‧氟離子選擇電極 32‧‧‧Fluoride ion selective electrode
34‧‧‧氟離子偵測槽 34‧‧‧Fluoride detection tank
36‧‧‧回流幫浦 36‧‧‧Reflow pump
40‧‧‧流體化床結晶槽 40‧‧‧ Fluidized bed crystallization tank
60‧‧‧pH控制器 60‧‧‧pH controller
62‧‧‧pH電極 62‧‧‧pH electrode
64‧‧‧隔膜式幫浦 64‧‧‧Separate pump
80‧‧‧沉澱池 80‧‧‧Sedimentation tank
90‧‧‧三相分離器 90‧‧‧Three-phase separator
AL‧‧‧鋁鹽溶液 AL‧‧‧Aluminium salt solution
ALF‧‧‧冰晶石結晶體 ALF‧‧‧Crylite crystal
L.1‧‧‧預定液位 L.1‧‧‧Predetermined liquid level
ND‧‧‧鹼液 ND‧‧‧ lye
S100‧‧‧含氟廢水處理方法 S100‧‧‧Fluorine wastewater treatment method
S110~S150‧‧‧步驟 S110~S150‧‧‧Steps
S122~S124‧‧‧步驟 S122~S124‧‧‧Steps
S132~S134‧‧‧步驟 S132~S134‧‧‧Steps
SF‧‧‧離子液 SF‧‧‧ ionic liquid
SL‧‧‧汙泥 SL‧‧‧Sludge
WA‧‧‧待處理水 WA‧‧‧ water to be treated
WF‧‧‧高濃度含氟廢水 WF‧‧‧high concentration fluorine-containing wastewater
WR‧‧‧低濃度含氟廢水 WR‧‧‧Low concentration fluorine-containing wastewater
第1圖係為本發明之含氟廢水處理方法的流程示意圖。 Fig. 1 is a schematic flow chart showing the method for treating fluorine-containing wastewater according to the present invention.
第2圖係為本發明之含氟廢水處理方法的系統示意圖。 Fig. 2 is a schematic view showing the system of the fluorine-containing wastewater treatment method of the present invention.
第3圖係為第1圖之氟離子偵測單元之偵測方式的流程示意圖。 Fig. 3 is a schematic flow chart showing the detection mode of the fluoride ion detecting unit of Fig. 1.
第4圖係為控制流體化床結晶槽內的pH值的流程示意圖。 Figure 4 is a schematic flow chart for controlling the pH in the fluidized bed crystallization tank.
第5圖係為第1圖之含氟廢水處理方法進一步的流程示意圖。 Fig. 5 is a schematic flow chart showing a further flow of the fluorine-containing wastewater treatment method of Fig. 1.
以下將參照隨附之圖式來描述本發明為達成目的所使用的技術手段與功效，而以下圖式所列舉之實施例僅為輔助說明，以利 貴審查委員瞭解，但本案之技術手段並不限於所列舉圖式。 The technical means and efficacy of the present invention for achieving the object will be described below with reference to the accompanying drawings, and the embodiments listed in the following drawings are only for the purpose of explanation, and are to be understood by the reviewing committee, but the technical means of the present invention are not Limited to the listed figures.
請參閱第1圖以及第2圖所示，其中第1圖係為本發明之含氟 廢水處理方法的流程示意圖。第2圖係為本發明之含氟廢水處理方法的系統示意圖。本實施例的含氟廢水處理方法S100，係以添加鋁鹽溶液與氟離子而形成冰晶石(Cryolite，Na3AlF6)結晶體，以達到處理含氟廢水及廢液的效果。所述含氟廢水處理方法S100，其至少包括以下步驟S110至S130。 Please refer to FIG. 1 and FIG. 2 , wherein FIG. 1 is the fluorine containing the present invention. Schematic diagram of the process of wastewater treatment. Fig. 2 is a schematic view showing the system of the fluorine-containing wastewater treatment method of the present invention. The fluorine-containing wastewater treatment method S100 of the present embodiment forms an ice crystal (Cryolite, Na3AlF6) crystal by adding an aluminum salt solution and fluoride ions to achieve the effect of treating the fluorine-containing wastewater and the waste liquid. The fluorine-containing wastewater treatment method S100 includes at least the following steps S110 to S130.
進行步驟S110，執行進水步驟至調勻槽20，其中所述進水步驟是將一待處理水WA以批次式操作進入至調勻槽20，調勻槽20內的待處理水WA包含一高濃度含氟廢水WF與一低濃度含氟廢水WR。需說明的是，低濃度含氟廢水WR的來源例如為經後續製程而得出的回收處理水。 In step S110, the water inflow step is performed to the mixing tank 20, wherein the water inflow step is to enter a water to be treated WA into the mixing tank 20 in a batch operation, and the water to be treated WA in the mixing tank 20 contains a high concentration. Fluorine-containing wastewater WF and a low concentration fluorine-containing wastewater WR. It should be noted that the source of the low-concentration fluorine-containing wastewater WR is, for example, the recovered treated water obtained by a subsequent process.
接著進行步驟S120，藉由一氟離子偵測單元30以控制調勻槽20內之待處理水WA之氟離子濃度，其中當待處理水WA之氟離子濃度至一預定濃度時，停止供高濃度含氟廢水WF進入至調勻槽20，當待處理水WA的水位達一預定液位L1時，停止供低濃度含氟廢水WR進入至調勻槽20。 Next, in step S120, the fluorine ion detecting unit 30 controls the fluoride ion concentration of the water to be treated WA in the mixing tank 20, wherein when the fluoride ion concentration of the water to be treated WA reaches a predetermined concentration, the high concentration is stopped. The fluorine-containing wastewater WF enters the mixing tank 20, and when the water level of the water to be treated WA reaches a predetermined liquid level L1, the low-concentration fluorine-containing wastewater WR is stopped from entering the mixing tank 20.
此外，本實施例還包括一液位計22，連接於氟離子偵測單元30。液位計22得以顯示調勻槽20內的水位，並將該水位訊息提供於氟離子偵測單元30。 In addition, the embodiment further includes a liquid level gauge 22 connected to the fluorine ion detecting unit 30. The level gauge 22 is capable of displaying the water level in the tempering tank 20 and providing the water level information to the fluorine ion detecting unit 30.
再來進行步驟S130，導入待處理水WA與一鋁鹽溶液AL至一流體化床結晶槽(fluidized crystallization bed)40，混合而得到一冰晶石結晶體(cryolite crystallization)40。 Further, in step S130, the water to be treated WA and the aluminum salt solution AL are introduced into a fluidized crystallization bed 40, and mixed to obtain a cryolite crystallization 40.
在上述的方法之下，本發明之含氟廢水處理方法，將待處理水WA以批次式操作進入至調勻槽20的步驟，詳細而言，將第一批的高濃度含氟廢水WF與低濃度含氟廢水WR導入至調勻槽20，而高濃度含氟廢水WF與低濃度含氟廢水WR混合成待處理水WA。當調勻槽20的待處理水WA的水 位達預定液位L1時，停止供低濃度含氟廢水WR進入至調勻槽20，與此同時，待處理水WA是持續導入至流體化床結晶槽40，直到調勻槽20的待處理水WA的水位未達預定液位L1，才再執行上述進水步驟，也就是將第二批的高濃度含氟廢水WF與低濃度含氟廢水WR導入至調勻槽20，如此將待處理水WA以批次式操作進入至調勻槽20的步驟，而非將待處理水WA連續操作而進入至調勻槽20。此外，藉由上述氟離子偵測單元30，當待處理水WA之氟離子濃度至預定濃度時，亦停止供高濃度含氟廢水WF進入至調勻槽20，如此一來，本實施例係以批次式的方式將待處理水WA導入至調勻槽20內控制調勻槽20內的水質之氟離子濃度維持在預定濃度內，以避免將待處理水WA以連續操作的方式進入至調勻槽20時水質之氟離子濃度變化過大而造成後續結晶效能不佳。 Under the above method, the fluorine-containing wastewater treatment method of the present invention, the step of operating the water to be treated WA into the mixing tank 20 by batch operation, in detail, the first batch of high-concentration fluorine-containing wastewater WF and The low-concentration fluorine-containing wastewater WR is introduced into the mixing tank 20, and the high-concentration fluorine-containing wastewater WF is mixed with the low-concentration fluorine-containing wastewater WR to form the water to be treated WA. When the water of the water to be treated WA of the tank 20 is adjusted When the predetermined liquid level L1 is reached, the low-concentration fluorine-containing wastewater WR is stopped from entering the mixing tank 20, and at the same time, the water to be treated WA is continuously introduced into the fluidized bed crystallization tank 40 until the water to be treated of the mixing tank 20 is treated. The water level is not up to the predetermined liquid level L1, and then the water inflow step is performed, that is, the second batch of the high-concentration fluorine-containing wastewater WF and the low-concentration fluorine-containing wastewater WR are introduced into the mixing tank 20, so that the water to be treated WA is The batch operation enters the step of the tempering tank 20 instead of continuously operating the water to be treated WA into the tempering tank 20. In addition, when the fluoride ion concentration of the water to be treated WA reaches a predetermined concentration, the high-concentration fluorine-containing wastewater WF is also stopped from entering the mixing tank 20, so that the embodiment is In a batch manner, the water to be treated WA is introduced into the mixing tank 20 to maintain the fluoride ion concentration of the water in the mixing tank 20 within a predetermined concentration, so as to prevent the water to be treated WA from entering the mixing tank 20 in a continuous operation manner. When the fluoride ion concentration of the water is changed too much, the subsequent crystallization efficiency is not good.
以下將進一步說明本實施例的含氟廢水處理方法S100中，對於氟離子偵測單元30的偵測方式。需說明的是，氟離子偵測單元30例如是用可程式控制器(Programmable Logic Controller,PLC)來執行，但本發明不以此為限。 The detection method of the fluorine ion detecting unit 30 in the fluorine-containing wastewater treatment method S100 of the present embodiment will be further described below. It should be noted that the fluorine ion detecting unit 30 is executed by, for example, a Programmable Logic Controller (PLC), but the invention is not limited thereto.
第3圖係為第1圖之氟離子偵測單元之偵測方式的流程示意圖。請參閱第3圖及第2圖。上述氟離子偵測單元30包括一氟離子選擇電極32與一氟離子偵測槽34。於藉由氟離子偵測單元30以控制調勻槽20內之待處理水WA之氟離子濃度的步驟S120中，含氟廢水處理方法S100更包括以下步驟S122至步驟S124。 Fig. 3 is a schematic flow chart showing the detection mode of the fluoride ion detecting unit of Fig. 1. Please refer to Figure 3 and Figure 2. The fluoride ion detecting unit 30 includes a fluorine ion selective electrode 32 and a fluorine ion detecting groove 34. In the step S120 of controlling the fluoride ion concentration of the water to be treated WA in the mixing tank 20 by the fluorine ion detecting unit 30, the fluorine-containing wastewater processing method S100 further includes the following steps S122 to S124.
進行步驟S122，導入高濃度含氟廢水WF及一離子液SF至氟離子偵測槽34。接著進行步驟S124，藉由氟離子選擇電極32以檢測氟離子 偵測槽34中的氟離子濃度。 Step S122 is performed to introduce high-concentration fluorine-containing wastewater WF and an ionic liquid SF to the fluorine ion detecting tank 34. Next, proceeding to step S124, the fluoride ion selective electrode 32 is used to detect the fluoride ion. The concentration of fluoride ions in the tank 34 is detected.
進行上述步驟之後，進行控制高濃度含氟廢水WF與離子液SF的比例為1：100的步驟。此外，在本實施例中，高濃度含氟廢水WF例如是含有20%之含氟廢水，但本發明不以此為限，端視實際情況而定。由於氟離子選擇電極32本身係無法承受如20%如此高濃度(或中濃度以上)含氟廢水，在控制與偵測期間例如是用幫浦24定量定速抽取調勻槽20內的高濃度含氟廢水WF，並確保高濃度含氟廢水WF與離子液SF的比例為1：100，易言之，本實施例係以稀釋高濃度含氟廢水WF的方式來偵測調勻槽20內高濃度含氟廢水WF之氟離子濃度。如此一來，不僅可達到偵測並確保氟離子濃度在一定的範圍內，還能夠延長氟離子選擇電極32的壽命，進而節省成本。 After the above steps, the step of controlling the ratio of the high-concentration fluorine-containing wastewater WF to the ionic liquid SF is 1:100. Further, in the present embodiment, the high-concentration fluorine-containing wastewater WF is, for example, a fluorine-containing wastewater containing 20%, but the present invention is not limited thereto, and it depends on the actual situation. Since the fluoride ion selective electrode 32 itself cannot withstand such a high concentration (or medium or higher concentration) of fluorine-containing wastewater, during the control and detection period, for example, the pump 24 is used to quantitatively select the high concentration in the homogenization tank 20 at a constant rate. Fluorine wastewater WF, and ensure that the ratio of high concentration fluorine-containing wastewater WF to ionic liquid SF is 1:100. In other words, this embodiment is to detect high concentration in the homogenization tank 20 by diluting high-concentration fluorine-containing wastewater WF. Fluoride ion concentration of fluorine-containing wastewater WF. In this way, not only the detection and ensuring that the concentration of the fluoride ion is within a certain range, but also the life of the fluoride ion selective electrode 32 can be prolonged, thereby saving cost.
另外，在本實施例中，流體化床結晶槽40中的鋁與氟的比例在0.8：6至1.2：6的範圍間。由於過量的鋁鹽溶液AL添加與不當的pH值環境，皆會降低回收之冰晶石結晶體ALF的純度。詳言之，當添加過量的鋁鹽溶液AL時，過量的鋁鹽溶液AL會沉澱，使得冰晶石結晶體ALF的純度下降。而當添加的鋁鹽溶液AL不足時，所形成的沉澱物才會以冰晶石結晶體ALF為主。進一步而言，當pH值大於7時，即便添加的鋁鹽溶液AL不足，所形成的沉澱物仍以氫氧化鋁為主。由此可知，如何讓流體化床結晶槽40中的鋁與氟的比例維持在0.8~1.2：6之間，以及適當的pH值環境，對於冰晶石結晶體ALF的純度與氟離子去除效率有很大的影響。 Further, in the present embodiment, the ratio of aluminum to fluorine in the fluidized bed crystallization tank 40 is in the range of 0.8:6 to 1.2:6. Due to the excessive addition of the aluminum salt solution AL and the improper pH environment, the purity of the recovered cryolite crystal ALF is lowered. In detail, when an excessive amount of the aluminum salt solution AL is added, the excess aluminum salt solution AL precipitates, so that the purity of the cryolite crystal ALF is lowered. When the added aluminum salt solution AL is insufficient, the formed precipitate will be dominated by cryolite crystal ALF. Further, when the pH is more than 7, even if the added aluminum salt solution AL is insufficient, the formed precipitate is mainly composed of aluminum hydroxide. It can be seen that how to maintain the ratio of aluminum to fluorine in the fluidized bed crystallization tank 40 between 0.8 and 1.2:6, and an appropriate pH environment, the purity of the cryolite crystal ALF and the fluoride ion removal efficiency are very high. Great impact.
關於控制鋁鹽溶液AL的添加，本實施例還包括，控制調勻槽20內之高濃度含氟廢水WF之氟離子濃度在3000±500mg/L，如此將高濃度含氟廢水WF導入至流體化床結晶槽40後，能確保並精準控制流體化床結晶 槽40內鋁與氟的穩定濃度比例，以得到高純度的冰晶石結晶體ALF。需說明的是，本實施例還包括以下步驟，使流體化床結晶槽40中的鋁與氟的比例在0.8：6至1.2：6的範圍間。 Regarding the control of the addition of the aluminum salt solution AL, the embodiment further includes: controlling the fluoride ion concentration of the high-concentration fluorine-containing wastewater WF in the mixing tank 20 to be 3000±500 mg/L, thus introducing the high-concentration fluorine-containing wastewater WF into the fluidization. After the bed crystallization tank 40, it can ensure and precisely control the fluidized bed crystallization The stable concentration ratio of aluminum to fluorine in the tank 40 is to obtain a high purity cryolite crystal ALF. It should be noted that the present embodiment further includes the following steps: the ratio of aluminum to fluorine in the fluidized bed crystallization tank 40 is in the range of 0.8:6 to 1.2:6.
第4圖係為控制流體化床結晶槽內的pH值的流程示意圖。請參閱第4圖及第2圖。在本實施例中，關於pH值的控制方式，於導入待處理水WA與鋁鹽溶液AL至流體化床結晶槽40，混合而得到冰晶石結晶體ALF的步驟S130，其還包括以下步驟S132至步驟S134。 Figure 4 is a schematic flow chart for controlling the pH in the fluidized bed crystallization tank. Please refer to Figure 4 and Figure 2. In this embodiment, with respect to the control method of the pH value, the step S130 is performed by introducing the water to be treated WA and the aluminum salt solution AL to the fluidized bed crystallization tank 40 to obtain the cryolite crystal ALF, which further includes the following step S132. Step S134.
進行步驟S132，藉由一pH控制器60以控制流體化床結晶槽40內的pH值達到一預定pH值，其中所述預定pH值的範圍例如在5.0~5.5間。接著進行步驟S134，當流體化床結晶槽40內的pH值未在預定pH值的範圍內時，導入一鹼液ND以使流體化床結晶槽40內的PH值達到預定pH值，其中本實施例所採用的鹼液ND例如是氫氧化鈉(NAOH)，但本發明不以此為限，端視實際使用情況而採用。 Step S132 is performed to control the pH value in the fluidized bed crystallization tank 40 to a predetermined pH value by a pH controller 60, wherein the predetermined pH value ranges, for example, between 5.0 and 5.5. Next, in step S134, when the pH value in the fluidized bed crystallization tank 40 is not within the range of the predetermined pH value, an alkali solution ND is introduced to bring the pH value in the fluidized bed crystallization tank 40 to a predetermined pH value. The lye ND used in the examples is, for example, sodium hydroxide (NAOH), but the invention is not limited thereto, and is employed depending on the actual use.
在本實施例中，可藉由一pH電極62即時偵測流體化床結晶槽40內水質性質變化(如pH值)，並經由pH控制器60控制一隔膜式幫浦64之開關，以控制鹼液ND導入至流體化床結晶槽40之流量，藉以控制流體化床結晶槽40內的pH值在5.0~5.5間。 In this embodiment, the water quality change (such as pH value) in the fluidized bed crystallization tank 40 can be immediately detected by a pH electrode 62, and the switch of the diaphragm type pump 64 is controlled via the pH controller 60 to control The flow rate of the lye ND to the fluidized bed crystallization tank 40 is controlled to control the pH in the fluidized bed crystallization tank 40 to be between 5.0 and 5.5.
第5圖係為第1圖之含氟廢水處理方法進一步的流程示意圖。請參閱第5圖及第2圖。在本實施例中，在上述步驟S130中，於導入待處理水WA與鋁鹽溶液AL至流體化床結晶槽40，混合而得到冰晶石結晶體ALF的步驟中，含氟廢水處理方S100更包括以下步驟S140至步驟S150。 Fig. 5 is a schematic flow chart showing a further flow of the fluorine-containing wastewater treatment method of Fig. 1. Please refer to Figure 5 and Figure 2. In the present embodiment, in the step S130, in the step of introducing the water to be treated WA and the aluminum salt solution AL to the fluidized bed crystallization tank 40 and mixing to obtain the cryolite crystal ALF, the fluorine-containing wastewater treatment unit S100 further includes The following steps S140 to S150.
接著進行步驟S140，進行一分離步驟，以得到低濃度含氟 廢水WR與汙泥SL。在本實施例中，分離而產生的汙泥SL會被排出。此外，上述步驟S140中，如第2圖所示，本實施例還包括一三相分離器90，其設於流體化床結晶槽40上方，主要是防止氣泡進入沉澱池80。需說明的是，在實際操作上，由於不需要添加混凝劑，因此，本實施例所產生的汙泥是非常少的。據此，本實施例除了能達到處理含氟廢水WF的目的之外，所得出的冰晶石結晶體ALF含水率在10%以下。並且，不需要添加混凝劑，因此能大幅降低排產生的汙泥SL量，更能減少棄置汙泥SL的成本。 Then proceeding to step S140, performing a separation step to obtain a low concentration fluorine Waste water WR and sludge SL. In the present embodiment, the separated sludge SL is discharged. Further, in the above step S140, as shown in Fig. 2, the present embodiment further includes a three-phase separator 90 disposed above the fluidized bed crystallization tank 40 to prevent bubbles from entering the sedimentation tank 80. It should be noted that, in actual operation, since the coagulant is not required to be added, the sludge produced in the present embodiment is very small. Accordingly, in addition to the purpose of treating the fluorine-containing wastewater WF, the obtained cryolite crystal ALF has a moisture content of 10% or less. Moreover, since it is not necessary to add a coagulant, the amount of sludge SL generated by the discharge can be greatly reduced, and the cost of the sludge SL can be reduced.
再來進行步驟S150，由氟離子偵測單元30控制一回流幫浦36，以將低濃度含氟廢水WR導入至調勻槽20。換言之，經上述步驟得出的回收處理水即可作為低濃度含氟廢水WR會在沉澱池80中，而若調勻槽20內之待處理水WA的水位未達預定液位L1，低濃度含氟廢水WR即可導入至調勻槽20。 Further, in step S150, a reflux pump 36 is controlled by the fluoride ion detecting unit 30 to introduce the low-concentration fluorine-containing wastewater WR into the mixing tank 20. In other words, the recovered treated water obtained by the above steps can be used as the low-concentration fluorine-containing wastewater WR in the sedimentation tank 80, and if the water level of the water to be treated WA in the mixing tank 20 does not reach the predetermined liquid level L1, the low concentration includes The fluorine wastewater WR can be introduced into the mixing tank 20.
綜上所述，本發明之含氟廢水處理方法，將高濃度含氟廢水與低濃度含氟廢水導入至調勻槽。當調勻槽的待處理水的水位達預定液位時，停止供低濃度含氟廢水進入至調勻槽，與此同時，待處理水是持續導入至流體化床結晶槽，直到調勻槽的待處理水的水位未達預定液位，才再次執行上述進水步驟。此外，藉由上述氟離子偵測單元，當待處理水之氟離子濃度至預定濃度時，亦停止供高濃度含氟廢水進入至調勻槽，如此一來，本發明係以批次式的方式將待處理水導入至調勻槽內控制調勻槽內的水質之氟離子濃度維持在預定濃度，以避免進水步驟時水質之氟離子濃度變化過大而造成後續結晶效能不佳。 In summary, the fluorine-containing wastewater treatment method of the present invention introduces a high-concentration fluorine-containing wastewater and a low-concentration fluorine-containing wastewater into a mixing tank. When the water level of the water to be treated in the mixing tank reaches a predetermined liquid level, the low-concentration fluorine-containing wastewater is stopped from entering the mixing tank, and at the same time, the water to be treated is continuously introduced into the fluidized bed crystallization tank until the mixing tank is to be treated. The above water inflow step is performed again if the water level of the water does not reach the predetermined level. In addition, when the fluorine ion concentration of the water to be treated reaches a predetermined concentration by the fluorine ion detecting unit, the high-concentration fluorine-containing wastewater is also stopped from entering the mixing tank, and thus the present invention is in a batch manner. The water to be treated is introduced into the mixing tank to control the fluoride ion concentration of the water in the mixing tank to be maintained at a predetermined concentration, so as to avoid excessive change of the fluoride ion concentration of the water in the water inlet step, resulting in poor subsequent crystallization efficiency.
雖然本發明已以實施例揭露如上，然其並非用以限定本發 明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，故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。 Although the present invention has been disclosed above by way of example, it is not intended to limit the present invention. It is to be understood that the scope of the invention is defined by the scope of the appended claims. quasi.
S100‧‧‧含氟廢水處理方法 S100‧‧‧Fluorine wastewater treatment method
S110~S130‧‧‧步驟 S110~S130‧‧‧Steps
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