TWI534094B - Treatment method by using fluidized-bed crystallization technology to remove phosphate from phosphate-containing wastewater - Google Patents

Treatment method by using fluidized-bed crystallization technology to remove phosphate from phosphate-containing wastewater Download PDF

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TWI534094B
TWI534094B TW104115833A TW104115833A TWI534094B TW I534094 B TWI534094 B TW I534094B TW 104115833 A TW104115833 A TW 104115833A TW 104115833 A TW104115833 A TW 104115833A TW I534094 B TWI534094 B TW I534094B
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phosphorus
phosphate
wastewater
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TW201641436A (en
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盧明俊
黃耀輝
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嘉藥學校財團法人嘉南藥理大學
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以流體化床結晶技術從含磷廢水中將磷移除之處理方法 Method for removing phosphorus from phosphorus-containing wastewater by fluidized bed crystallization technology

本發明關於一種從廢水中將磷移除之處理方法,尤指一種以流體化床結晶技術從含磷廢水中將磷移除之處理方法。 The invention relates to a treatment method for removing phosphorus from waste water, in particular to a treatment method for removing phosphorus from phosphorus-containing wastewater by fluidized bed crystallization technology.

隨著這幾年來科技快速發展,隨之而來的是嚴重的環境汙染、空氣汙染、水質汙染,造成生態被嚴重破壞。其中最嚴重的末過於因工業發展快速而造成大量的工業廢水隨意排放,這些工業廢水中多含有大量的重金屬及無機汙染物等,如果人類食用過多恐造成病變等問題。 With the rapid development of science and technology over the past few years, serious environmental pollution, air pollution, and water pollution have caused serious damage to the ecology. The most serious of these is due to the rapid industrial development, a large amount of industrial wastewater is arbitrarily discharged. These industrial wastewaters contain a lot of heavy metals and inorganic pollutants, etc., if human consumption is too much, it may cause diseases and other problems.

過去的除磷技術主要有化學混凝、吸附法、生物處理及流體化床結晶。其中,化學混凝技術是以金屬鹽類作為沉澱劑,加入鹼液調整適當的pH值來與磷酸根反應形成固體析出溶液,並配合高分子絮凝劑的添加,以共沉澱的機制來達到除磷目的。化學混凝沉澱雖然具有操作簡單且除磷效果佳的優點,但是在除磷過程中需要添加大量的藥劑,其產生的固體廢棄物含水率高,固體純度低,會造成後續處理的困擾及增加處理汙泥的成本。吸附法是在含磷溶液中添加吸附劑,由於吸附材表面與吸附質帶相反電荷,所 以在正負電荷作用下相互吸引,但不直接與吸附材表面產生鏈接,而是藉由靜電附著於吸附材表面。吸附法雖然具有操作簡單的優點,但是吸附材飽和後需要進行脫附提濃度或運棄,且吸附材再生次數有限,因而尚屬開發階段。生物處理為污水廠主要的除磷方法,藉由厭氧池與好氧池的串聯,讓微生物能夠吸收水中的磷,達到除磷目的。生物除磷法無需額外添加藥劑,操作成本相對較低,但是生物除磷法無法處理高濃度的含磷溶液,且會產生大量的生物污泥,仍然不是一個完美的除磷技術。 The past phosphorus removal technologies mainly include chemical coagulation, adsorption, biological treatment and fluidized bed crystallization. Among them, the chemical coagulation technology uses metal salts as a precipitant, adding an alkali solution to adjust the appropriate pH value to react with the phosphate to form a solid precipitation solution, and with the addition of the polymer flocculant, the mechanism of coprecipitation is used to achieve the removal. Phosphorus purpose. Although the chemical coagulation sedimentation has the advantages of simple operation and good phosphorus removal effect, a large amount of chemicals need to be added in the phosphorus removal process, and the solid waste generated by the solid waste has high water content and low solid purity, which may cause troubles and increase of subsequent treatment. The cost of treating sludge. The adsorption method is to add an adsorbent to the phosphorus-containing solution, because the surface of the adsorbent is opposite to the adsorbed charge, They attract each other under the action of positive and negative charges, but do not directly link with the surface of the adsorbent, but are attached to the surface of the adsorbent by static electricity. Although the adsorption method has the advantages of simple operation, the adsorption material needs to be desorbed to extract concentration or transport after being saturated, and the number of regeneration of the adsorbent material is limited, so it is still in the development stage. Biological treatment is the main method of phosphorus removal in the sewage plant. By connecting the anaerobic tank and the aerobic tank in series, the microorganism can absorb the phosphorus in the water to achieve the purpose of phosphorus removal. The biological phosphorus removal method does not require additional additives, and the operation cost is relatively low. However, the biological phosphorus removal method cannot handle the high concentration of the phosphorus-containing solution, and a large amount of biological sludge is generated, which is still not a perfect phosphorus removal technology.

近年來,流體化床結晶技術用於除磷已受到重視,而逐漸應用在污水廠。流體化床結晶除磷技術除了保有化學混凝沉澱技術的高效率優點外,因僅操作在低過飽和度,可大大減少化學藥劑的使用。此外,流體化床結晶技術產生之結晶珠,因粒徑大且含水率不高,因而,無需再加入絮凝劑或進行污泥再脫水的程序,在廢棄物的處理上可節省不少成本。習用『流體化床結晶技術』的處理裝置主要包括一反應槽(即流體化床),該反應槽內具有擔體。欲處理之廢水由該反應槽之底部向上流動,使得擔體達到一定上流速度而流體化,且該反應槽連接藥劑入口用以送入藥劑,使得廢水中的污染物在流體化床中的擔體上結晶,藉以去除廢水中的陰離子或金屬離子,並回收可再利用的金屬顆粒。然而,習用的『流體化床結晶技術』需要在反應槽內添加擔體(如矽砂、磚粉等)來進行結晶,造成金屬結晶體中含有擔體成分,晶體的純度不佳,影響其再利用的價值。 In recent years, fluidized bed crystallization technology has been paid attention to in phosphorus removal, and it has gradually been applied in sewage plants. In addition to the high efficiency advantages of chemical coagulation and sedimentation technology, fluidized bed crystallization and phosphorus removal technology can greatly reduce the use of chemicals because it operates at low supersaturation. In addition, the crystal beads produced by the fluidized bed crystallization technology have a large particle size and a low water content, so that there is no need to add a flocculant or a sludge re-dewatering process, which can save a lot of cost in the disposal of waste. The treatment device of the "fluidized bed crystallization technique" mainly comprises a reaction tank (i.e., a fluidized bed) having a support therein. The waste water to be treated flows upward from the bottom of the reaction tank, so that the support fluidizes at a certain upward flow speed, and the reaction tank is connected to the chemical inlet for feeding the medicament, so that the pollutant in the waste water is carried in the fluidized bed. Crystallization on the body to remove anions or metal ions from the wastewater and recover the reusable metal particles. However, the conventional "fluidized bed crystallization technology" requires the addition of a support (such as strontium sand, brick powder, etc.) to the reaction tank to cause crystallization, which causes the metal crystal body to contain a support component, and the purity of the crystal is not good, which affects it. The value of utilization.

緣此,本發明之主要目的在於提供一種新的流體化床結晶技術, 可從含磷廢水中將磷移除,此處理方法可解決在現有混凝技術所需佔地空間大且污泥產生量大的問題,因其需要橫向串連快混池、慢混池、沉澱池及污泥脫水機等設備。此外,此處理方法不需要添加任何異質擔體來進行結晶,因而,可提高操作上的便利性且所取得的結晶顆粒純度會提升,同時也增加流體化床結晶顆粒再利用及資源化的效益。 Accordingly, the main object of the present invention is to provide a new fluidized bed crystallization technique. Phosphorus can be removed from phosphorus-containing wastewater. This treatment method can solve the problem of large space occupied by existing coagulation technology and large amount of sludge production, because it requires horizontally connected fast mixing tanks, slow mixing pools, Equipment such as sedimentation tanks and sludge dewatering machines. In addition, this treatment method does not require the addition of any heterogeneous support for crystallization, thereby improving the convenience of operation and improving the purity of the obtained crystal particles, and also increasing the benefits of recycling and recycling of the fluidized bed crystal particles. .

根據本發明之以流體化床結晶技術從含磷廢水中將磷移除之處理方法,首先提供一流體化床反應槽,該反應槽具有一下段及一上段,該下段設有一廢水進流口與一藥劑進流口,該上段設有一出水口,該下段與該上段之間具有一迴流管路;接著,將含磷廢水與結晶藥劑個別從該廢水進流口與該藥劑進流口引入該流體化床反應槽內混合,其中結晶藥劑含有鈣離子且鈣離子對該含磷廢水中的磷酸根離子之莫爾濃度比控制在1.0:1.0至2.0:1.0之間,該進流廢水的酸鹼值(pH)控制在6至9之間;接著,使與結晶藥劑混合的含磷廢水由該反應槽的下段向該反應槽的上段流動且經由該迴流管路迴流至下段以進行循環,使得含磷廢水中的磷酸根離子與結晶藥劑中的鈣離子反應以形成磷酸鈣結晶顆粒。 According to the present invention, a method for removing phosphorus from a phosphorus-containing wastewater by a fluidized bed crystallization technique, firstly providing a fluidized bed reaction tank having a lower section and an upper section, the lower section being provided with a wastewater inlet port And a medicament inlet port, the upper section is provided with a water outlet, and a circulation line is provided between the lower section and the upper section; then, the phosphorus-containing wastewater and the crystallizing agent are separately introduced from the wastewater inlet port and the medicament inlet port Mixing in the fluidized bed reaction tank, wherein the crystallization agent contains calcium ions and the molar concentration ratio of calcium ions to the phosphate ions in the phosphorus-containing wastewater is controlled between 1.0:1.0 and 2.0:1.0, and the inflowing wastewater is The pH value is controlled between 6 and 9; then, the phosphorus-containing wastewater mixed with the crystallization agent flows from the lower portion of the reaction tank to the upper portion of the reaction tank and is returned to the lower portion via the reflux line for circulation The phosphate ions in the phosphorus-containing wastewater are reacted with calcium ions in the crystallization agent to form calcium phosphate crystal particles.

根據本發明,進流的磷酸根離子濃度也直接影響除磷處理之效率,在一較佳實施例中,進流的磷酸根離子濃度控制在1000mg/L至1500mg/L之間。 According to the present invention, the influent phosphate ion concentration also directly affects the efficiency of the phosphorus removal treatment. In a preferred embodiment, the influent phosphate ion concentration is controlled between 1000 mg/L and 1500 mg/L.

在一最佳實施例中,鈣離子對該含磷廢水中的磷酸根離子之莫爾濃度比約為2.0:1.0,進流廢水的pH值為在7至9之間,進流的磷酸根離子濃度為1500mg/L。 In a preferred embodiment, the molar ratio of calcium ions to phosphate ions in the phosphorus-containing wastewater is about 2.0:1.0, and the pH of the influent wastewater is between 7 and 9, the influent phosphate The ion concentration was 1500 mg/L.

在一最佳實施例中,鈣離子對該含磷廢水中的磷酸根離子之莫爾濃度比約為1.4:1.0,進流廢水的pH值為在7至9之間,進流的磷酸根離子濃度為1500mg/L。 In a preferred embodiment, the molar ratio of calcium ions to phosphate ions in the phosphorus-containing wastewater is about 1.4:1.0, and the pH of the influent wastewater is between 7 and 9, the influent phosphate The ion concentration was 1500 mg/L.

關於本發明之其它目的、優點及特徵,將可由以下較佳實施例的詳細說明並參照所附圖式來了解。 Other objects, advantages and features of the present invention will become apparent from

10‧‧‧反應槽 10‧‧‧Reaction tank

12‧‧‧下段 12‧‧‧ lower section

14‧‧‧上段 14‧‧‧上段

16‧‧‧廢水進流口 16‧‧‧ Wastewater inlet

18‧‧‧藥劑進流口 18‧‧‧Pharmaceutical inflow

20‧‧‧出水口 20‧‧‧Water outlet

22‧‧‧迴流管路 22‧‧‧Return line

24‧‧‧酸鹼值檢測器 24‧‧‧pH detector

26‧‧‧幫浦 26‧‧‧

28‧‧‧幫浦 28‧‧‧

30‧‧‧含磷廢水 30‧‧‧Fluorine-containing wastewater

32‧‧‧結晶藥劑 32‧‧‧Crystal Pharmacy

圖1係繪示根據本發明一實施例之流體化床反應槽的示意圖。 1 is a schematic view of a fluidized bed reaction tank in accordance with an embodiment of the present invention.

圖2(a)、(b)與(c)個別繪示在1500ppm磷酸根離子(PO4 -3)進流濃度及鈣離子對磷酸根離子之莫爾濃度比(Ca+2:PO4 -3)=1.0:1.0的操作條件下,不同酸鹼值(pH6、pH9)之進流廢水相對磷去除率(phosphate removal%)、磷轉化率(phosphate conversion%)與所收集顆粒量(mass of granules)的關係圖。 Figure 2 (a), (b) and (c) individually show the influent concentration of 1500 ppm phosphate ion (PO 4 -3 ) and the molar concentration ratio of calcium ion to phosphate ion (Ca +2 : PO 4 - 3 )=1.0:1.0 operating conditions, different pH values (pH6, pH9) of influent wastewater relative phosphorus removal rate (phosphate removal%), phosphorus conversion rate (phosphate conversion%) and the amount of collected particles (mass of Diagram of granules).

圖3(a)、(b)與(c)個別繪示在1500ppm磷酸根離子進流濃度及Ca+2:PO4 -3=1.0:1.0的操作條件下,不同酸鹼值(pH6、pH7、pH9、pH11)之進流廢水相對磷去除率、磷轉化率與所收集顆粒量的關係圖。 Figure 3 (a), (b) and (c) individually show different pH values (pH 6, pH 7) under operating conditions of 1500 ppm phosphate ion influent concentration and Ca +2 : PO 4 -3 = 1.0: 1.0. , pH9, pH11) of the influent wastewater relative phosphorus removal rate, phosphorus conversion rate and the amount of collected particles.

圖4(a)、(b)與(c)個別繪示在1500ppm磷酸根離子進流濃度及pH9之進流廢水的操作條件下,不同鈣離子對磷酸根離子之莫爾濃度比(Ca+2:PO4 -3=1.0:1.0、1.2:1.0、1.4:1.0)相對磷去除率、磷轉化率與所收集顆粒量的關係圖。 Figure 4 (a), (b) and (c) individually show the Mohr concentration ratio of different calcium ions to phosphate ions under the operating conditions of 1500 ppm phosphate ion influent concentration and pH 9 influent wastewater (Ca + 2 : PO 4 -3 = 1.0: 1.0, 1.2: 1.0, 1.4: 1.0) A plot of relative phosphorus removal rate, phosphorus conversion rate, and amount of collected particles.

圖5(a)、(b)與(c)個別繪示在Ca+2:PO4 -3=1.2:1.0及pH9之進流廢水的操作條件下,不同進流的磷酸根離子濃度( 500mg/L、1000mg/L、1500mg/L PO4 -3)相對磷去除率、磷轉化率與所收集顆粒量的關係圖。 Figures 5(a), (b) and (c) show the phosphate ion concentration of different influent (500mg) under the operating conditions of influent wastewater with Ca +2 : PO 4 -3 = 1.2:1.0 and pH9. /L, 1000 mg/L, 1500 mg/L PO 4 -3 ) A plot of relative phosphorus removal rate, phosphorus conversion rate and amount of collected particles.

本發明在於提出一種以流體化床結晶技術從含磷廢水中將磷移除之處理方法,該處理方法係利用結晶造粒方式將含磷廢水中的磷移除,且取得的結晶顆粒可以進一步再利用。在該處理方法中,首先提供一流體化床反應槽10(見圖1),該反應槽10具有一管狀下段12及一管狀上段14,該上段14的外徑大於該下段12的外徑。該下段12設有一廢水進流口16與一藥劑進流口18,該上段14設有一出水口20,該下段12與該上段14之間具有一迴流管路22。在本實施例中,該反應槽10的下段12底部為圓錐形,有助於迴流流力分散均勻。在該出水口20的地方設置一酸鹼值(pH值)檢測器24以監測出流口pH值,同時採集水樣進行水質分析。 The present invention is directed to a treatment method for removing phosphorus from phosphorus-containing wastewater by a fluidized bed crystallization technique, which utilizes crystallization granulation to remove phosphorus from the phosphorus-containing wastewater, and the obtained crystalline particles can be further Reuse. In the treatment method, a fluidized bed reaction tank 10 (see Fig. 1) is first provided, the reaction tank 10 having a tubular lower section 12 and a tubular upper section 14, the upper section 14 having an outer diameter larger than the outer diameter of the lower section 12. The lower section 12 is provided with a waste water inlet 16 and a medicament inlet 18, the upper section 14 is provided with a water outlet 20, and the lower section 12 and the upper section 14 have a return line 22. In the present embodiment, the bottom portion of the lower portion 12 of the reaction tank 10 has a conical shape to facilitate uniform dispersion of the return flow force. A pH value detector 24 is provided at the water outlet 20 to monitor the pH of the flow port while collecting water samples for water quality analysis.

接著,利用幫浦26、28個別將含磷廢水30與結晶藥劑32從該廢水進流口16與該藥劑進流口18引入該反應槽10的下段12內混合。 Next, the phosphorus-containing wastewater 30 and the crystallization agent 32 are separately introduced into the lower stage 12 of the reaction tank 10 from the wastewater inlet port 16 and the chemical inlet port 18 by means of the pumps 26 and 28.

接著,使與結晶藥劑32混合的含磷廢水30由該下段12向該上段14流動且經由該迴流管路22迴流至該下段12以進行循環,使得含磷廢水30中的磷酸根離子與結晶藥劑32反應。在本實施例中,該結晶藥劑32為含鈣離子藥劑(例如氯化鈣藥劑),利用鈣離子與含磷廢水30中的磷酸根離子反應產生磷酸鈣結晶顆粒,且將過飽和度控制在適當範圍,使含磷廢水30在流體化床反應槽10內進行顆粒化反應以除去含磷廢水30中的磷酸根離子。 Next, the phosphorus-containing wastewater 30 mixed with the crystallization agent 32 is caused to flow from the lower stage 12 to the upper stage 14 and is returned to the lower stage 12 via the return line 22 for circulation, so that the phosphate ions and crystals in the phosphorus-containing wastewater 30 are crystallization. The agent 32 reacts. In the present embodiment, the crystallization agent 32 is a calcium ion-containing agent (for example, a calcium chloride agent), and calcium ions are reacted with phosphate ions in the phosphorus-containing wastewater 30 to produce calcium phosphate crystal particles, and the supersaturation is controlled appropriately. In the range, the phosphorus-containing wastewater 30 is subjected to a granulation reaction in the fluidized bed reaction tank 10 to remove phosphate ions in the phosphorus-containing wastewater 30.

根據本發明之處理方法,進流廢水的酸鹼值(pH值)、鈣離子對 磷酸根離子之莫爾濃度比(Ca+2:PO4 -3)、以及進流的磷酸根離子濃度將分別影響含磷廢水30中的磷去除率與磷轉化率(液態轉化為固態)。依據試驗結果,進流廢水的酸鹼值最好控制在7至9之間,鈣離子對磷酸根離子之莫爾濃度比(Ca+2:PO4 -3)最好控制在1.0:1.0至1.4:1.0之間,進流的磷酸根離子濃度最好控制在1000至1500mg/hr之間。 According to the treatment method of the present invention, the pH value of the influent wastewater (pH value), the molar ratio of calcium ions to phosphate ions (Ca +2 : PO 4 -3 ), and the influent phosphate ion concentration will The phosphorus removal rate and the phosphorus conversion rate (liquid to solid state) in the phosphorus-containing wastewater 30 are respectively affected. According to the test results, the pH value of the influent wastewater is preferably controlled between 7 and 9, and the molar ratio of calcium ions to phosphate ions (Ca +2 : PO 4 -3 ) is preferably controlled at 1.0:1.0 to Between 1.4 and 1.0, the influent phosphate ion concentration is preferably controlled between 1000 and 1500 mg/hr.

請參照圖2(a)與圖2(b),其分別繪示不同pH值的進流廢水在顆粒生長穩定後的磷去除率與磷轉化率比較,操作條件為進流廢水的pH值分別為6、9,結晶藥劑32的鈣離子相對含磷廢水30的磷酸根離子的莫爾濃度比(Ca+2:PO4 -3)固定為1.0:1.0,進流的磷酸根離子濃度為1500mg/L。其中磷去除率係比較不同pH值之反應槽內之消耗的總磷酸根離子濃度及出流水之過濾後濃度。從圖2(a)中可以看出在60小時的操作時間結束後,pH值6的磷去除率為49.62%,而pH值9的磷去除率為73.39%;從圖2(b)中可以看出pH值6的磷轉化率為53.01%,而pH值9的磷轉化率為73.36%;從圖2(c)中可以看出pH值6所收集的顆粒量為17.47克,而pH值9所收集的顆粒量為61.03克。圖2(a)、(b)、(c)中顯示當pH從6增加至9時,磷去除率、磷轉化率及收集的顆粒量都有急劇增加,因而,進流廢水的pH值大大影響到磷去除率以及所獲得的結晶顆粒量。亦即,增加進流廢水的PH值,將有更多的磷酸氢根(HPO4 -2)與磷酸根(PO4 -3)來與鈣離子反應以形成更多的磷酸鈣化合物,而且不僅提高顆粒形式的量,也鼓勵晶體生長,例如在pH9中獲得的顆粒最大尺寸大於0.840毫米,而在pH6收集的顆粒最大尺寸約為0.590毫米。 Referring to FIG. 2(a) and FIG. 2(b), respectively, the phosphorus removal rate and the phosphorus conversion rate of the influent wastewater with different pH values after the particle growth stability are respectively compared, and the operating conditions are the pH values of the influent wastewater respectively. 6 and 9, the molar concentration of the calcium ion of the crystallizing agent 32 relative to the phosphate ion of the phosphorus-containing wastewater 30 (Ca +2 : PO 4 -3 ) is fixed at 1.0:1.0, and the influent phosphate ion concentration is 1500 mg. /L. The phosphorus removal rate is a comparison of the total phosphate ion concentration consumed in the reaction tank with different pH values and the filtered concentration of the outflow water. It can be seen from Fig. 2(a) that after the end of the 60-hour operation time, the phosphorus removal rate of pH 6 is 49.62%, and the phosphorus removal rate of pH 9 is 73.39%; from Fig. 2(b) It can be seen that the phosphorus conversion rate of pH 6 is 53.01%, and the phosphorus conversion rate of pH 9 is 73.36%; from Fig. 2(c), it can be seen that the amount of particles collected at pH 6 is 17.47 g, and the pH value is 9 The amount of particles collected was 61.03 g. Figure 2 (a), (b), (c) shows that when the pH is increased from 6 to 9, the phosphorus removal rate, the phosphorus conversion rate, and the amount of collected particles all increase sharply. Therefore, the pH of the influent wastewater is greatly increased. Affects the phosphorus removal rate and the amount of crystal particles obtained. That is, increasing the pH of the influent wastewater will cause more hydrogen phosphate (HPO 4 -2 ) and phosphate (PO 4 -3 ) to react with calcium ions to form more calcium phosphate compounds, and not only Increasing the amount of particulate form also encourages crystal growth, for example, the maximum size of the particles obtained at pH 9 is greater than 0.840 mm, while the maximum size of particles collected at pH 6 is about 0.590 mm.

請參照圖3(a)與圖3(b),其分別繪示不同pH值的進流廢水在顆粒生長穩定後的磷去除率與磷轉化率的另一實施例比較,其操作條件為進流廢水的pH值分別為6、7、9、11,結晶藥劑32的鈣離子相對含磷廢水30的磷酸根離子的莫爾濃度比(Ca+2:PO4 -3)固定為1.2:1.0,進流的磷酸根離子濃度為1500mg/L。從圖3(a)中可以看出在60小時的操作時間結束後,最低磷去除率與轉化率是在pH6,其中pH值6的磷去除率為56.40%,pH值7的磷去除率為85.95%;pH值9的磷去除率為88.37%,而pH值11的磷去除率在9至18小時的操作期間最高,但24小時後,降低為73.39%。從圖3(b)中可以看出pH值6的磷轉化率為59.80%,pH值7的磷轉化率為90.31%,pH值9的磷轉化率為90.80%,而pH值11的磷轉化率為74.81%。從圖3(c)中可以看出pH值6所收集的顆粒量為23.91克,pH值7所收集的顆粒量為71.29克,pH值9所收集的顆粒量為76.43克,而pH值11所收集的顆粒量下降到59.79克。在圖3(a)、(b)、(c)中顯示當pH值從6增加至9時,磷去除率、磷轉化率及收集的顆粒量同樣都有急劇增加(因為有更多的磷酸根離子可與鈣離子反應),但是,當pH從9增加至11時,磷去除率、磷轉化率以及收集的顆粒量會下降(因為有更多的晶核位置的存在),在此pH值不是由晶體成長來主導磷去除率,是由晶核位置來主導磷去除率。 Please refer to FIG. 3( a ) and FIG. 3( b ) respectively, which respectively illustrate another embodiment of the phosphorus removal rate and phosphorus conversion rate of the inflow wastewater with different pH values after the particle growth is stabilized, and the operating conditions are The pH values of the flowing wastewater were 6, 7, 9, and 11, respectively, and the molar concentration of the calcium ion of the crystallizing agent 32 relative to the phosphate ion of the phosphorus-containing wastewater 30 (Ca +2 : PO 4 -3 ) was fixed at 1.2:1.0. The influent phosphate ion concentration was 1500 mg/L. It can be seen from Fig. 3(a) that after the end of the 60-hour operation time, the lowest phosphorus removal rate and conversion rate are at pH 6, wherein the phosphorus removal rate of pH 6 is 56.40%, and the phosphorus removal rate of pH 7 is 85.95%; the phosphorus removal rate of pH 9 was 88.37%, while the phosphorus removal rate of pH 11 was highest during the operation period of 9 to 18 hours, but decreased to 73.39% after 24 hours. It can be seen from Fig. 3(b) that the phosphorus conversion rate of pH 6 is 59.80%, the phosphorus conversion rate of pH 7 is 90.31%, the phosphorus conversion rate of pH 9 is 90.80%, and the phosphorus conversion of pH value 11 is obtained. The rate is 74.81%. It can be seen from Fig. 3(c) that the amount of particles collected at pH 6 is 23.91 g, the amount of particles collected at pH 7 is 71.29 g, and the amount of particles collected at pH 9 is 76.43 g, while pH 11 The amount of particles collected dropped to 59.79 grams. In Figures 3(a), (b), and (c), when the pH is increased from 6 to 9, the phosphorus removal rate, phosphorus conversion rate, and amount of collected particles also increase sharply (because there is more phosphoric acid). Root ions can react with calcium ions), however, as the pH increases from 9 to 11, the phosphorus removal rate, phosphorus conversion rate, and amount of collected particles decrease (because there are more nucleation sites present) at this pH. The value is not dominated by crystal growth to dominate the phosphorus removal rate, which is dominated by the nucleation site.

請參照圖4(a)與圖4(b),其分別繪示不同鈣離子對磷酸根離子之莫爾濃度比(Ca+2:PO4 -3=1.0:1.0、1.2:1.0、1.4:1.0)在顆粒生長穩定後的磷去除率與磷轉化率(液態轉化為固態)比較。操作條件為進流廢水的pH值固定為9,進流的磷酸根離子濃 度為1500mg/L。其中磷去除率係比較不同pH值之反應槽內之消耗的總磷酸根離子濃度及出流水之過濾後濃度。從圖4(a)、圖4(b)中可以看出在60小時的操作時間結束後,Ca+2:PO4 -3=1.0:1.0的磷去除率與磷轉化率約為72.39%,Ca+2:PO4 -3=1.2:1.0的磷去除率與磷轉化率約為88.37%,Ca+2:PO4 -3=1.4:1.0的磷去除率與磷轉化率約為97.09%。可見,隨著鈣離子對磷酸根離子之莫爾濃度比的增加,磷去除率與磷轉化率會提高(因為有更多的鈣離子可與磷酸根離子反應)。從圖4(c)中可以看出Ca+2:PO4 -3=1.0:1.0所收集的顆粒量為61.03克,Ca+2:PO4 -3=1.2:1.0所收集的顆粒量為76.43克,而Ca+2:PO4 -3=1.4:1.0所收集的顆粒量為136.86克,且顆粒的最大尺寸大於1.00毫米。由於有更多的鈣離子存在,所以隨著鈣離子對磷酸根離子之莫爾濃度比的增加,所收集的顆粒量也會增加。 Please refer to FIG. 4(a) and FIG. 4(b), respectively, which illustrate the Mohr concentration ratio of different calcium ions to phosphate ions (Ca +2 : PO 4 -3 = 1.0: 1.0, 1.2: 1.0, 1.4: 1.0) The phosphorus removal rate after the particle growth is stabilized is compared with the phosphorus conversion rate (liquid to solid state). The operating conditions were such that the pH of the influent wastewater was fixed at 9, and the influent phosphate ion concentration was 1500 mg/L. The phosphorus removal rate is a comparison of the total phosphate ion concentration consumed in the reaction tank with different pH values and the filtered concentration of the outflow water. It can be seen from Fig. 4(a) and Fig. 4(b) that after the end of the 60-hour operation time, the phosphorus removal rate and the phosphorus conversion rate of Ca +2 : PO 4 -3 = 1.0: 1.0 are about 72.39%. The phosphorus removal rate and phosphorus conversion rate of Ca +2 :PO 4 -3 = 1.2:1.0 are about 88.37%, and the phosphorus removal rate and phosphorus conversion rate of Ca +2 :PO 4 -3 = 1.4:1.0 are about 97.09%. It can be seen that as the molar ratio of calcium ions to phosphate ions increases, the phosphorus removal rate and phosphorus conversion rate increase (because more calcium ions can react with phosphate ions). It can be seen from Fig. 4(c) that the amount of particles collected by Ca +2 :PO 4 -3 =1.0:1.0 is 61.03 g, and the amount of particles collected by Ca +2 :PO 4 -3 =1.2:1.0 is 76.43. Grams, while Ca +2 : PO 4 -3 = 1.4: 1.0 The amount of particles collected was 136.86 grams, and the largest size of the particles was greater than 1.00 mm. Since more calcium ions are present, the amount of collected particles increases as the molar ratio of calcium ions to phosphate ions increases.

請參照圖5(a)與圖5(b),其分別繪示不同進流的磷酸根離子濃度(500mg/L、1000mg/L、1500mg/L PO4 -3)在顆粒生長穩定後的磷去除率與磷轉化率(液態轉化為固態)比較。操作條件為進流廢水的pH值固定為9,鈣離子對磷酸根離子的莫爾濃度比(Ca+2:PO4 -3)固定為1.2:1.0。從圖5(a)、圖5(b)中可以看出在60小時的操作時間結束後,磷酸根離子濃度500mg/L的磷去除率與磷轉化率約為46.16%,磷酸根離子濃度1000mg/L的磷去除率與磷轉化率約為64.84%,磷酸根離子濃度1500mg/L的磷去除率與磷轉化率約為88.37%。隨著磷酸根離子濃度的增加,磷去除率與磷轉化率會提高(因為有更多的鈣離子可與磷酸根離子反應)。從實施例的試驗中發現,在最低磷酸根離子濃度範圍中的 離子難以相互反應,最終將以溶解或未反應的形式脫逃到流化床反應器中,導致磷去除率與磷轉化率相對較低。從圖5(c)中可以看出,磷酸根離子濃度500mg/L所收集的顆粒量為5.06克,磷酸根離子濃度1000mg/L所收集的顆粒量為23.90克,磷酸根離子濃度1500mg/L所收集的顆粒量為76.43克。因而,提高磷酸根離子濃度,將使所收集的顆粒量增加,同時具有更高的磷去除率。 Please refer to FIG. 5( a ) and FIG. 5( b ) respectively, which respectively show the phosphoric acid ion concentration (500 mg/L, 1000 mg/L, 1500 mg/L PO 4 -3 ) of different inflows after the particle growth is stable. The removal rate is compared to the phosphorus conversion rate (liquid to solid). The operating conditions were such that the pH of the influent wastewater was fixed at 9, and the molar concentration ratio of calcium ions to phosphate ions (Ca +2 : PO 4 -3 ) was fixed at 1.2:1.0. It can be seen from Fig. 5(a) and Fig. 5(b) that after the end of the 60-hour operation time, the phosphate removal rate and the phosphorus conversion rate of the phosphate ion concentration of 500 mg/L are about 46.16%, and the phosphate ion concentration is 1000 mg. The phosphorus removal rate and phosphorus conversion rate of /L are about 64.84%, and the phosphorus removal rate and phosphorus conversion rate of phosphate ion concentration 1500 mg/L are about 88.37%. As the concentration of phosphate ions increases, the phosphorus removal rate and phosphorus conversion rate increase (because more calcium ions can react with phosphate ions). It was found from the experiments of the examples that the ions in the range of the minimum phosphate ion concentration are difficult to react with each other and eventually escape to the fluidized bed reactor in a dissolved or unreacted form, resulting in a relatively high phosphorus removal rate and phosphorus conversion rate. low. It can be seen from Fig. 5(c) that the amount of particles collected by the phosphate ion concentration of 500 mg/L is 5.06 g, the amount of particles collected by the phosphate ion concentration of 1000 mg/L is 23.90 g, and the phosphate ion concentration is 1500 mg/L. The amount of particles collected was 76.43 grams. Thus, increasing the phosphate ion concentration will increase the amount of collected particles while having a higher phosphorus removal rate.

由以上結果可知,本發明的處理方法可用來從含磷廢水中將磷有效地移除,且可減少化學藥劑的使用;更者,該處理方法不需要在流體化床反應槽內使用擔體,因而所獲得的處理效率與結晶顆粒純度高,具有較高的利用潛力。再者,本發明的處理方法係利用操作條件與反應槽設計的改變使晶體在流體化床反應槽內形成,其中進流廢水的酸鹼值(pH)控制在6至9之間,且鈣離子對該含磷廢水中的磷酸根離子之莫爾濃度比控制在1.0:1.0至1.4:1.0之間,因而,有更多的磷酸根離子與更多的鈣離子反應,藉以提高磷的去除效率與結晶造粒率。 From the above results, the treatment method of the present invention can be used to effectively remove phosphorus from phosphorus-containing wastewater and reduce the use of chemicals; moreover, the treatment method does not require the use of a support in a fluidized bed reaction tank. Therefore, the treatment efficiency obtained is high and the purity of the crystal particles is high, and the utilization potential is high. Furthermore, the treatment method of the present invention utilizes changes in operating conditions and reaction tank design to form crystals in a fluidized bed reaction tank, wherein the pH of the influent wastewater is controlled between 6 and 9, and calcium is The molar concentration ratio of ions to the phosphate ions in the phosphorus-containing wastewater is controlled between 1.0:1.0 and 1.4:1.0, and thus, more phosphate ions react with more calcium ions, thereby increasing phosphorus removal. Efficiency and crystallization granulation rate.

在前述說明書中,本發明僅是就特定實施例做描述,而依本發明的特徵仍可有多種變化或修改。是以,對於熟悉此項技藝人士可作之明顯替換與修改,仍將併入於本發明所主張的專利範圍之內。 In the foregoing specification, the invention has been described in terms of a particular embodiment, and various changes or modifications may be made in accordance with the features of the invention. Therefore, obvious substitutions and modifications may be made by those skilled in the art, and will still be incorporated in the scope of the claimed invention.

10‧‧‧反應槽 10‧‧‧Reaction tank

12‧‧‧下段 12‧‧‧ lower section

14‧‧‧上段 14‧‧‧上段

16‧‧‧廢水進流口 16‧‧‧ Wastewater inlet

18‧‧‧藥劑進流口 18‧‧‧Pharmaceutical inflow

20‧‧‧出水口 20‧‧‧Water outlet

22‧‧‧迴流管路 22‧‧‧Return line

24‧‧‧酸鹼值檢測器 24‧‧‧pH detector

26‧‧‧幫浦 26‧‧‧

28‧‧‧幫浦 28‧‧‧

30‧‧‧含磷廢水 30‧‧‧Fluorine-containing wastewater

32‧‧‧結晶藥劑 32‧‧‧Crystal Pharmacy

Claims (4)

一種以流體化床結晶技術從含磷廢水中將磷移除之處理方法,包含:提供一流體化床反應槽,其具有一下段及一上段,該下段設有一廢水進流口與一藥劑進流口,該上段設有一出水口,該下段與該上段之間具有一迴流管路,該反應槽內不具有擔體;將含磷廢水與結晶藥劑個別從該廢水進流口與該藥劑進流口引入該流體化床反應槽內混合,其中進流的磷酸根離子濃度控制在1000mg/L至1500mg/L之間,結晶藥劑含有鈣離子且鈣離子對該含磷廢水中的磷酸根離子之莫爾濃度比控制在1.0:1.0至1.4:1.0之間,該進流廢水的酸鹼值(pH)控制在7至9之間;以及使與結晶藥劑混合的含磷廢水由該反應槽的下段向該反應槽的上段流動且經由該迴流管路迴流至下段以進行循環,使得含磷廢水中的磷酸根離子與結晶藥劑中的鈣離子反應以形成結晶顆粒。 A method for removing phosphorus from a phosphorus-containing wastewater by a fluidized bed crystallization technique, comprising: providing a fluidized bed reaction tank having a lower section and an upper section, wherein the lower section is provided with a wastewater inlet and a medicament a flow port, the upper section is provided with a water outlet, and a return line is provided between the lower section and the upper section, the reaction tank does not have a support; the phosphorus-containing wastewater and the crystallizing agent are separately from the waste water inlet and the medicament The flow port is introduced into the fluidized bed reaction tank, wherein the influent phosphate ion concentration is controlled between 1000 mg/L and 1500 mg/L, and the crystallizing agent contains calcium ions and calcium ions are phosphate ions in the phosphorus-containing wastewater. The molar concentration ratio is controlled between 1.0:1.0 and 1.4:1.0, the pH value of the influent wastewater is controlled between 7 and 9; and the phosphorus-containing wastewater mixed with the crystallization agent is used in the reaction tank The lower portion flows to the upper portion of the reaction tank and is returned to the lower portion via the reflux line for circulation, so that phosphate ions in the phosphorus-containing wastewater react with calcium ions in the crystallizing agent to form crystal particles. 如申請專利範圍第1項所述之處理方法,其中結晶藥劑為氯化鈣。 The treatment method according to claim 1, wherein the crystallization agent is calcium chloride. 如申請專利範圍第1項所述之處理方法,其中鈣離子對該含磷廢水中的磷酸根離子之莫爾濃度比為1.2:1.0,進流廢水的pH值為9,進流的磷酸根離子濃度為1500mg/L。 The treatment method according to claim 1, wherein the calcium ion concentration ratio of the phosphate ion in the phosphorus-containing wastewater is 1.2:1.0, the pH of the influent wastewater is 9, and the inflowing phosphate The ion concentration was 1500 mg/L. 如申請專利範圍第1項所述之處理方法,其中鈣離子對該含磷廢水中的磷酸根離子之莫爾濃度比為1.4:1.0,進流廢水的pH值為9 ,進流的磷酸根離子濃度為1500mg/L。 The treatment method according to claim 1, wherein the calcium ion concentration ratio of the phosphate ion in the phosphorus-containing wastewater is 1.4:1.0, and the pH of the influent wastewater is 9 The influent phosphate ion concentration was 1500 mg/L.
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CN109205829A (en) * 2018-09-08 2019-01-15 天津大学 The method of film assisting crystallisation technique MAC selective removal and the copper in recycle-water

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109205829A (en) * 2018-09-08 2019-01-15 天津大学 The method of film assisting crystallisation technique MAC selective removal and the copper in recycle-water

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