TWI612014B - method for treating boron-containing wastewater using fluidized-bed ?homogeneous granulation technique - Google Patents

method for treating boron-containing wastewater using fluidized-bed ?homogeneous granulation technique Download PDF

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TWI612014B
TWI612014B TW105112535A TW105112535A TWI612014B TW I612014 B TWI612014 B TW I612014B TW 105112535 A TW105112535 A TW 105112535A TW 105112535 A TW105112535 A TW 105112535A TW I612014 B TWI612014 B TW I612014B
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boron
wastewater
coagulant
ions
hydrogen peroxide
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TW201738185A (en
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黃耀輝
玄東 吳
黃烱秦
林睿彥
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萬年清環境工程股份有限公司
國立成功大學
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Abstract

本發明有關一種以流體化床均質顆粒化技術處理含硼廢水之方法。此方法包含使用過氧化氫與硼離子反應,以及在流體化床反應器中添加混凝劑(氯化鈣)的均質顆粒化步驟,並且產生含水率低於5%、粒徑大於0.5 mm的過硼酸鈣均質顆粒,達到減容的效果,利於後續的回收再利用。The invention relates to a method for treating boron-containing wastewater by a fluidized bed homogeneous granulation technique. The method comprises the steps of: reacting hydrogen peroxide with boron ions, and adding a coagulant (calcium chloride) to the fluidized bed reactor, and producing a moisture content of less than 5% and a particle size greater than 0.5 mm. Calcium perborate homogenized particles, to achieve the effect of volume reduction, which is conducive to subsequent recycling and reuse.

Description

以流體化床均質顆粒化技術處理含硼廢水之方法Method for treating boron-containing wastewater by fluidized bed homogenization granulation technology

本發明關於一種含硼廢水之回收再利用的處理方法,特別是關於一種以低含水率顆粒方式將含硼量由數百到數千ppm以上的含硼廢水中的硼回收的氧化/顆粒化技術,具有減容及高純度等利於後續再利用的優點。The invention relates to a method for treating recycling of boron-containing wastewater, in particular to an oxidation/granulation of boron recovered from boron-containing wastewater having a boron content of several hundred to several thousand ppm or more in a low water content particle manner. The technology has the advantages of reduced capacity and high purity, which are beneficial for subsequent recycling.

硼的相關化合物在現代工業中有廣泛的應用,舉凡火力發電廠、核電廠、玻璃、陶瓷釉料廠,或是TFT-LCD廠製程中所使用的大量硼酸,都有含硼化物的身影,它還常用於洗衣用的漂白粉、洗衣劑,農業所使用的肥料、殺蟲劑等。而其釋放的廢棄物往往會進入環境當中,尤其含硼廢水的回收再利用處理技術目前尚未成熟,並沒有辦法有效的回收高純度低含水率的含硼鹽類。Boron related compounds have a wide range of applications in modern industry. The boricides are used in thermal power plants, nuclear power plants, glass, ceramic glaze plants, or a large amount of boric acid used in TFT-LCD manufacturing processes. It is also commonly used in laundry bleaching powders, laundry detergents, fertilizers used in agriculture, and pesticides. The wastes released by them often enter the environment. In particular, the recycling and treatment technology of boron-containing wastewater is not yet mature, and there is no way to effectively recover high-purity and low-water content boron-containing salts.

目前的除硼技術約可大略分為6種,分別為化學沉澱法、離子交換法、吸附法、逆滲透、萃取法與電化學法,但各個方法都有其限制。離子交換法、吸附法與逆滲透都只適用於低濃度的含硼廢液,離子交換法與吸附法擁有極佳的選擇性,且市面上已有商用的樹脂與吸附材可以購買,但多半要價不斐且再生不易。逆滲透是目前商轉最廣泛的技術,但都僅限於低濃度的含硼廢水或是海水淡化,尤其為了增加除硼效果,pH往往要調至10以上以產生帶負價的硼酸根離子,但若硬度過高往往會造成薄膜結垢的問題。電化學法適合用於低濃度含硼廢水,在處理高濃度含硼廢水上的效果就會驟降,且在應用上會有犧牲性陽極的成本考量,設備成本較高。化學沉澱法與萃取法都十分適合處理高濃度的含硼廢水,萃取法所使用的溶劑多為雙醇類,但溶劑的毒性及後續的處理相對棘手;而化學沉澱法在業界中是最廣為接受的技術,但是傳統的混凝沉澱法往往需要高溫的條件來模擬水熱法,以產生難溶性的物種。The current boron removal technology can be roughly divided into six types, namely chemical precipitation method, ion exchange method, adsorption method, reverse osmosis, extraction method and electrochemical method, but each method has its limitations. The ion exchange method, adsorption method and reverse osmosis are only suitable for low concentration boron-containing waste liquid. The ion exchange method and the adsorption method have excellent selectivity, and commercially available resins and adsorbents can be purchased, but most of them are commercially available. The asking price is not high and the regeneration is not easy. Reverse osmosis is currently the most widely traded technology, but it is limited to low concentration of boron-containing wastewater or seawater desalination, especially in order to increase the boron removal effect, the pH is often adjusted to more than 10 to produce a negative borate ion. However, if the hardness is too high, it will cause the problem of film fouling. The electrochemical method is suitable for low-concentration boron-containing wastewater, and the effect on the treatment of high-concentration boron-containing wastewater will be drastically reduced, and the cost of the sacrificial anode will be considered in application, and the equipment cost is high. Both chemical precipitation method and extraction method are very suitable for the treatment of high concentration boron-containing wastewater. The solvent used in the extraction method is mostly dihydric alcohol, but the toxicity and subsequent treatment of the solvent are relatively difficult; and the chemical precipitation method is the most widely used in the industry. Acceptable techniques, but traditional coagulation precipitation methods often require high temperature conditions to simulate hydrothermal methods to produce poorly soluble species.

美國專利第6039789號(Removal of boron and fluoride from water)為一整合程序:包括從廢水中去除B及F化合物後,再利用產生之污泥從含硫化物(sulfide)或硫(sulfur)之金礦中回收金之方法,其中B及F之處理以外加含Mg之氫氧化物予以去除。美國專利第5925255號(Method and apparatus for high efficiency reverse osmosis operation)為利用RO薄膜技術進行超純水處理之方法,先經前處理去除硬度鹼度後,再提升pH值達10.5以上以去除B、Si及TOC等物質之程序。美國專利第4800042號(Radioactive waste water treatment)主要為核廢料減量之處理程序,廢水經加鹼調整pH後進行蒸發濃縮,並加入氫氧化鈣以產生硼酸鹽,最後之蒸發濃縮液或以水泥固化處理或以蒸發乾燥處理。US Patent No. 6039789 (Removal of boron and fluoride from water) is an integrated procedure that involves removing B and F compounds from wastewater and then using the resulting sludge from a sulfur or sulfur A method of recovering gold in a mine, wherein the treatment of B and F is carried out by adding a hydroxide containing Mg. US Patent No. 5,925,255 (Method and apparatus for high efficiency reverse osmosis operation) is a method for treating ultrapure water by RO thin film technology. After pre-treatment to remove hardness alkalinity, the pH value is raised above 10.5 to remove B. Procedures for substances such as Si and TOC. U.S. Patent No. 4,0004,402 (Radioactive waste water treatment) is mainly for the treatment of nuclear waste reduction. The wastewater is adjusted to pH by adding alkali, and then concentrated by evaporation, and calcium hydroxide is added to produce borate, and finally the concentrated liquid is solidified by solidification. Treated or treated by evaporative drying.

針對含硼廢水的上述問題,在本案發明人研發後,提出公告號538008號「含硼廢水的處理方法」加以解決。該處理方法利用二道添加氧化劑(例如過氧化氫)及混凝劑(例如氫氧化鈣)之氧化/混凝處理,大幅降低硼含量後,再配合離子交換樹脂法或逆滲透法去除殘留低濃度部份。然而,該處理方法需要雙重混凝步驟才能將數千ppm的硼降至約15 ppm。In response to the above problems of the boron-containing wastewater, after the inventors of the present invention developed, the method of "treatment of boron-containing wastewater" No. 538008 was proposed. The treatment method utilizes an oxidation/coagulation treatment of adding an oxidizing agent (for example, hydrogen peroxide) and a coagulant (for example, calcium hydroxide) to greatly reduce the boron content, and then the ion exchange resin method or the reverse osmosis method is used to remove the residual low. Concentration part. However, this treatment requires a double coagulation step to reduce thousands of ppm of boron to about 15 ppm.

本案發明人針對公告號538008號「含硼廢水的處理方法」進一步研發後,提出申請號104100411「高濃度含硼廢水之處理方法」加以解決,該處理方法利用一道預處理步驟和一道沉澱步驟即可將數千ppm的硼有效低將硼移除至海水硼的平均濃度5 ppm以下,但依然有後續大量沉澱物的處理問題,其含水率高,體積大,在處理上需要額外設備與費用。The inventor of the present invention further developed the application method No. 538008 "Process for the treatment of boron-containing wastewater", and proposed the application method 104100411 "Process for treating high-concentration boron-containing wastewater", which utilizes a pretreatment step and a precipitation step. Thousands of ppm of boron can be effectively low to remove boron to an average concentration of 5 ppm below seawater boron, but there are still problems with the subsequent treatment of a large amount of sediment, which has a high water content, a large volume, and requires additional equipment and costs in processing. .

緣此,本發明之主要目的在於提供一種以流體化床均質顆粒化技術處理含硼廢水之方法,該方法可用來從硼含量由數百到數千ppm以上的廢水中有效地將硼以過硼酸鹽類形式回收,且該方法結合流體化床均質顆粒化技術,可產生含水率低的過硼酸鹽均質顆粒,達到減容及高純度的效果。Accordingly, the main object of the present invention is to provide a method for treating boron-containing wastewater by a fluidized bed homogenization granulation technique, which can be used to effectively treat boron from waste water having a boron content of several hundred to several thousand ppm or more. The borate form is recovered, and the method combines the fluidized bed homogenization granulation technology to produce perborate homogenous particles with low water content, thereby achieving the effects of volume reduction and high purity.

根據本發明之一實施例,此以流體化床均質顆粒化技術處理含硼廢水之方法係包括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混凝劑進流口,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;將過氧化氫與含硼廢水施予連續進料且在一混合槽內混合反應,該含硼廢水濃度介於100至15000 ppm之間;將與該過氧化氫反應後的含硼廢水與另一股混凝劑個別從該廢水進流口與該混凝劑進流口引入該反應槽的下段中混和;以及將與該混凝劑混合的含硼廢水由該下段向該上段流動且經由該迴流管路迴流至該下段以進行循環,使得含硼廢水中的硼離子與該混凝劑反應以產生過硼酸鹽均質顆粒。According to an embodiment of the invention, the method for treating boron-containing wastewater by a fluidized bed homogenization granulation technique comprises 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 coagulant inlet port, the upper section is provided with a water outlet, and a reflux line is provided between the lower section and the upper section; hydrogen peroxide and boron-containing wastewater are continuously fed and mixed in a mixing tank, The concentration of the boron-containing wastewater is between 100 and 15000 ppm; the boron-containing wastewater reacted with the hydrogen peroxide and the other coagulant are separately introduced from the wastewater inlet port and the coagulant inlet port. Mixing the lower portion of the reaction tank; and flowing the boron-containing wastewater mixed with the coagulant from the lower portion to the upper portion and returning to the lower portion via the return line to circulate, so that boron ions in the boron-containing wastewater and the The coagulant reacts to produce perborate homogeneous particles.

在一實施例中,該混凝劑為含鈣化合物,該混凝劑中的鈣離子相對於含硼廢水的硼離子的莫爾濃度比最好介於0.5至2之間,其值影響過硼酸鹽類的結晶效率及回收硼的效果。In one embodiment, the coagulant is a calcium-containing compound, and the molar concentration of the calcium ions in the coagulant relative to the boron ions of the boron-containing wastewater is preferably between 0.5 and 2. The crystallization efficiency of borate and the effect of recovering boron.

此以流體化床均質顆粒化技術處理含硼廢水之方法更包含一過氧化氫濃度控制步驟,使過氧化氫濃度在顆粒化反應中維持穩定。在一實施例中,該過氧化氫相對於含硼廢水中的硼離子的莫爾濃度比介於0.5至4之間。在一較佳實施例中,該過氧化氫相對於含硼廢水中的硼離子的莫爾濃度比為1-4。The method for treating boron-containing wastewater by fluidized bed homogenization granulation technology further comprises a hydrogen peroxide concentration control step to maintain the hydrogen peroxide concentration stable in the granulation reaction. In one embodiment, the Mohr concentration ratio of the hydrogen peroxide relative to the boron ions in the boron-containing wastewater is between 0.5 and 4. In a preferred embodiment, the Mohr concentration ratio of the hydrogen peroxide to boron ions in the boron-containing wastewater is 1-4.

此以流體化床均質顆粒化技術處理含硼廢水之方法更包含一出流水酸鹼值控制步驟,使流體化床均質顆粒化過程維持在適當酸鹼值,方能維持較高的顆粒化回收率。在一實施例中,該出流水酸鹼值控制在8至11之間。在一較佳實施例中,該出流水酸鹼值控制在9至10.6之間。The method for treating boron-containing wastewater by fluidized bed homogenization granulation technology further comprises a flow acid pH control step to maintain a proper pH value of the fluidized bed homogenization granulation process to maintain high granulation recovery. rate. In one embodiment, the outflow water pH is controlled between 8 and 11. In a preferred embodiment, the pH of the effluent water is controlled between 9 and 10.6.

此以流體化床均質顆粒化技術處理含硼廢水之方法更包含一顆粒床高控制步驟,床高若高於一定的高度,能使過硼酸鹽結晶回收率有效提升。在一較佳實施例中,該顆粒床高控制在高於40公分。The method for treating boron-containing wastewater by fluidized bed homogenization granulation technology further comprises a particle bed high control step, and if the bed height is higher than a certain height, the perborate crystal recovery rate can be effectively improved. In a preferred embodiment, the bed height is controlled above 40 cm.

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

本發明主要在於提出一種以流體化床均質顆粒化技術處理含硼廢水之方法,其用於回收含硼廢水中的硼,並且以高純度、低含水率的過硼酸鹽均質顆粒為產物,能有效達到污染物減容及提高純度的效果,優於傳統混凝沉澱法,利於未來回收再利用。在該方法中,首先提供一流體化床反應槽10(見第4圖),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與一混凝劑進流口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底部為錐形,有助於迴流流力分散均勻。在該出水口20處設置一酸鹼值(pH值)檢測器(未圖示)以監測出流口pH值,同時採集水樣進行水質分析。The invention mainly provides a method for treating boron-containing wastewater by fluidized bed homogenization granulation technology, which is used for recovering boron in boron-containing wastewater, and uses high-purity, low-water content perborate homogenous particles as a product, Effectively achieve the effect of reducing the volume of pollutants and improving the purity, which is superior to the traditional coagulation and sedimentation method, which is beneficial for recycling and reuse in the future. In this method, a fluidized bed reaction tank 10 (see FIG. 4) is first provided. The reaction tank 10 has a tubular lower section 12 and a tubular upper section 14, the upper section 14 having an outer diameter greater than the outer diameter of the lower section 12. The lower section 12 is provided with a waste water inlet 16 and a coagulant 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 is tapered to facilitate uniform dispersion of the return flow force. A pH value detector (not shown) is provided at the water outlet 20 to monitor the pH of the outlet, and a water sample is collected for water quality analysis.

接著,利用幫浦24、26個別將過氧化氫28與含硼廢水30施予一連續進料步驟在一混合槽32內充分混合反應。接著,利用幫浦34、36個別將與過氧化氫反應後的含硼廢水30與另一股混凝劑38從該廢水進流口16與該混凝劑進流口18引入該反應槽10的下段12中均勻混和。接著,使與混凝劑38混合的含硼廢水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,使得含硼廢水30中的硼離子與混凝劑38進行顆粒化反應以產生過硼酸鹽固體微粒,並利用該反應槽10的截面積不同以及回流循環,使固體微粒透過足夠碰撞形成含水率低的均質顆粒,並使用連續進料使含硼廢水30中的硼以過硼酸鹽形式回收以除去含硼廢水30中的硼離子。在本實施例中,該混凝劑38為含鈣化合物(例如氯化鈣),但實施時不限於此。Next, the hydrogen peroxide 28 and the boron-containing wastewater 30 are individually subjected to a continuous feeding step by a pump 24, 26 to sufficiently mix the reaction in a mixing tank 32. Next, the boron-containing wastewater 30 reacted with hydrogen peroxide and the other coagulant 38 are separately introduced into the reaction tank 10 from the wastewater inlet port 16 and the coagulant inlet port 18 by means of the pumps 34 and 36. The lower section 12 is uniformly mixed. Next, the boron-containing wastewater 30 mixed with the coagulant 38 is flowed from the lower section 12 to the upper section 14 and returned to the lower section 12 via the return line 22 for circulation, so that boron ions in the boron-containing wastewater 30 are mixed. The condensing agent 38 performs a granulation reaction to generate perborate solid particles, and utilizes the cross-sectional area of the reaction tank 10 and the reflux cycle to allow the solid particles to pass through sufficient collision to form homogeneous particles having a low water content, and to use continuous feed to contain Boron in the boron wastewater 30 is recovered as perborate to remove boron ions from the boron-containing wastewater 30. In the present embodiment, the coagulant 38 is a calcium-containing compound (for example, calcium chloride), but is not limited thereto.

根據本發明之方法,所添加的過氧化氫相對於含硼廢水30中的硼離子的莫爾濃度比(H 2O 2/B)、混凝劑38中的鈣離子相對於含硼廢水30的硼離子的莫爾濃度比(Ca/B)、出流水酸鹼值(pHe)、以及顆粒床高(流體化床靜止時的顆粒堆積在反應器內的高度)將分別影響含硼廢水30中的硼離子去除率與顆粒穩定後的顆粒化率。依據試驗結果,該H 2O 2/B的莫爾濃度比最好介於0.5~4之間,該Ca/B的莫爾濃度比最好介於0.5~1.5之間,該出流水酸鹼值(pHe)最好控制在8至11之間,而顆粒床高最好控制在高於40公分。 According to the method of the present invention, the Mohr concentration ratio (H 2 O 2 /B) of the added hydrogen peroxide relative to the boron ions in the boron-containing wastewater 30, and the calcium ions in the coagulant 38 relative to the boron-containing wastewater 30 The Mohr concentration ratio (Ca/B) of the boron ion, the pH value of the outflow water (pHe), and the height of the particle bed (the height of the particles accumulated in the reactor when the fluidized bed is at rest) will affect the boron-containing wastewater 30, respectively. The boron ion removal rate in the medium and the granulation rate after the particles are stabilized. According to the test result, the Mohr concentration ratio of the H 2 O 2 /B is preferably between 0.5 and 4, and the Mo/concentration ratio of the Ca/B is preferably between 0.5 and 1.5. The value (pHe) is preferably controlled between 8 and 11, and the particle bed height is preferably controlled to be higher than 40 cm.

請參照第1圖,其係繪示在流體化床均質顆粒化步驟中控制滯留時間(含硼廢水30進入到該反應槽10且從上方出流口20流出所需時間)為18 min ,且在H 2O 2/B=2、出流水酸鹼值(pHe)=10、顆粒床高=80 cm、初始硼濃度為1000 ppm的操作條件下,其CR[B]r、TR[B]r會隨Ca/B改變而變化,其中Ca/B=0.5~0.7效果較佳。 Referring to FIG. 1 , it is shown that the residence time is controlled in the fluidized bed homogenization granulation step (the time required for the boron-containing wastewater 30 to enter the reaction vessel 10 and flow out from the upper outlet 20 ) is 18 min, and CR[B]r, TR[B] under operating conditions of H 2 O 2 /B=2, pH of outlet water (pHe)=10, particle bed height=80 cm, initial boron concentration of 1000 ppm r will change with Ca/B change, and Ca/B=0.5~0.7 is better.

請參照第2圖,其係繪示在流體化床均質顆粒化步驟中控制滯留時間為18min,且在H 2O 2/B=2、Ca/B=0.7、顆粒床高=80 cm、初始硼濃度為1000 ppm的操作條件下,其CR[B]r、TR[B]r會隨出流水酸鹼值(pHe)改變而變化,其中當pHe高於10.6時,代表反應器負荷量過大,而顆粒化率大幅下降,操作上pHe應控制低於10.6。 Please refer to Fig. 2, which shows that the residence time is 18 min in the fluidized bed homogenization granulation step, and the H 2 O 2 / B= 2, Ca/B=0.7, particle bed height=80 cm, initial Under the operating conditions of boron concentration of 1000 ppm, CR[B]r and TR[B]r will change with the pH value of the flowing water. When the pHe is higher than 10.6, the reactor load is too large. While the granulation rate drops drastically, the pHe should be controlled below 10.6.

請參照第3圖,其係繪示在流體化床均質成核沉澱步驟中控制滯留時間為18min,且在H 2O 2/B=2、Ca/B=0.7、pHe=9.6、初始硼濃度為1010 ppm的操作條件下,其CR[B]r、TR[B]r會隨顆粒床高改變而變化,其中當顆粒床高低於50 cm時,代表顆粒所提供的反應表面積提供不足,造成顆粒化率大幅下降,操作上應使顆粒床高高於50 cm。 Please refer to FIG. 3, which shows that the residence time is 18 min in the fluidized bed homogenization nucleation precipitation step, and the H 2 O 2 /B= 2, Ca/B=0.7, pHe=9.6, initial boron concentration. Under the operating conditions of 1010 ppm, CR[B]r and TR[B]r will change with the change of particle bed height. When the particle bed height is lower than 50 cm, it means that the reaction surface area provided by the particles is insufficient. The granulation rate is greatly reduced and the operation should be such that the particle bed height is higher than 50 cm.

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 12.下段10. Reaction tank 12. Lower section

14.上段 16.廢水進流口14. Upper section 16. Wastewater inlet

18.混凝劑進流口 20.出水口18. Coagulant inlet 20. Water outlet

22.迴流管路 24、26.幫浦22. Return line 24, 26. Pump

28.過氧化氫 30.含硼廢水28. Hydrogen peroxide 30. Boron-containing wastewater

32.混合槽 34、36.幫浦32. Mixing tank 34, 36. Pump

38.混凝劑38. Coagulant

第1圖係繪示流體化床均質顆粒化步驟中不同鈣/硼(Ca/B)比對去除率、結晶率、殘留硼濃度的關係圖;其中[B]t 代表過濾後的溶液硼濃度、[B]c代表未過濾的溶液硼濃度、TR[B]r代表硼的總去除率、CR[B]r代表硼的顆粒化率。Figure 1 is a graph showing the relationship between the removal ratio, crystallization rate and residual boron concentration of different calcium/boron (Ca/B) ratios in the fluidized bed homogenization granulation step; where [B]t represents the boron concentration of the filtered solution. [B]c represents the unfiltered solution boron concentration, TR[B]r represents the total removal rate of boron, and CR[B]r represents the granulation rate of boron.

第2圖係繪示流體化床均質顆粒化步驟中不同出流水酸鹼值(pH值)對去除率、顆粒化率、殘留硼濃度的關係圖。Figure 2 is a graph showing the relationship between the pH value of different outflow waters, the granulation rate, and the residual boron concentration in the fluidized bed homogenization granulation step.

第3圖係繪示流體化床均質顆粒化步驟中不同靜置顆粒床高對去除率、顆粒化率、殘留硼濃度的關係圖。Figure 3 is a graph showing the relationship between the bed height of different static particles in the fluidized bed homogenization granulation step, the removal rate, the granulation rate, and the residual boron concentration.

第4圖係繪示根據本發明一實施例之流體化床反應槽的示意圖。4 is a schematic view of a fluidized bed reaction tank in accordance with an embodiment of the present invention.

10.反應槽 12.下段 14.上段 16.廢水進流口 18.混凝劑進流口 20.出水口 22.迴流管路 24、26.幫浦 28.過氧化氫 30.含硼廢水 32.混合槽 34、36.幫浦 38.混凝劑10. Reaction tank 12. Lower section 14. Upper section 16. Wastewater inlet port 18. Coagulant inlet port 20. Water outlet 22. Return line 24, 26. Pump 28. Hydrogen peroxide 30. Boron-containing wastewater 32 Mixing tank 34, 36. Pump 38. Coagulant

Claims (8)

以流體化床均質顆粒化技術處理含硼廢水之方法,包括: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混凝劑進流口,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;將過氧化氫與含硼廢水施予連續進料且在一混合槽內混合反應,該含硼廢水濃度介於100至15000ppm之間,該過氧化氫相對於含硼廢水中的硼離子的莫爾濃度比介於0.5至4之間;將與該過氧化氫反應後的含硼廢水與另一股混凝劑個別從該廢水進流口與該混凝劑進流口引入該反應槽的下段中混和;以及將與該混凝劑混合的含硼廢水由該下段向該上段流動且經由該迴流管路迴流至該下段以進行循環,使得含硼廢水中的硼離子與該混凝劑反應以產生過硼酸鹽均質顆粒,其中該混凝劑為含鈣化合物,該混凝劑中的鈣離子相對於含硼廢水的硼離子的莫爾濃度比介於0.5至2之間,其中顆粒床高控制在高於40公分,其中出流水酸鹼值控制在8至11之間。 The method for treating boron-containing wastewater by fluidized bed homogenization granulation technology comprises: providing a fluidized bed reaction tank having a lower section and an upper section, wherein the lower section is provided with a wastewater inlet port and a coagulant inlet port, The upper section is provided with a water outlet, and a reflux line is provided between the lower section and the upper section; the hydrogen peroxide and the boron-containing wastewater are continuously fed and mixed in a mixing tank, and the concentration of the boron-containing wastewater is between 100 Between 15000 ppm, the Mohr concentration ratio of the hydrogen peroxide relative to the boron ions in the boron-containing wastewater is between 0.5 and 4; the boron-containing wastewater after reacting with the hydrogen peroxide and another coagulant Individually mixing from the wastewater inflow port and the coagulant inlet into the lower portion of the reaction tank; and flowing the boron-containing wastewater mixed with the coagulant from the lower section to the upper section and refluxing through the reflux line To the lower stage for recycling, the boron ions in the boron-containing wastewater are reacted with the coagulant to produce perborate homogeneous particles, wherein the coagulant is a calcium-containing compound, and the calcium ions in the coagulant are relative to Boron ion of boron wastewater Ratios in the range between 0.5 and 2, wherein the particle bed height 40 cm higher than the control, wherein the water pH is controlled between 8-11. 如申請專利範圍第1項所述之方法,其中該混凝劑為含鈣化合物,該混凝劑中的鈣離子相對於含硼廢水的硼離子的莫爾濃度比介於0.5至1.5之間。 The method of claim 1, wherein the coagulant is a calcium-containing compound, and a molar concentration of calcium ions in the coagulant relative to boron ions of the boron-containing wastewater is between 0.5 and 1.5. . 如申請專利範圍第1項所述之方法,其中該出流水酸鹼值控制在8至10.6之間。 The method of claim 1, wherein the outflow water pH is controlled between 8 and 10.6. 如申請專利範圍第1項所述之方法,其中該過氧化氫相對於含硼廢水中的硼離子的莫爾濃度比為1-4,該混凝劑中的鈣離子相對於含硼廢水的硼離子的莫爾濃度比介於0.5至0.7之間。 The method of claim 1, wherein the molar ratio of the hydrogen peroxide to the boron ions in the boron-containing wastewater is 1-4, and the calcium ions in the coagulant are relative to the boron-containing wastewater. The molar concentration ratio of boron ions is between 0.5 and 0.7. 如申請專利範圍第1項所述之方法,其中該過氧化氫相對於含硼廢水中的硼離子的莫爾濃度比為2,該混凝劑中的鈣離子相對於含硼廢水的硼離子的莫爾濃度比為0.7,該出流水酸鹼值控制在9至10.6之間。 The method of claim 1, wherein the molar ratio of the hydrogen peroxide to the boron ions in the boron-containing wastewater is 2, and the calcium ions in the coagulant are relative to the boron ions in the boron-containing wastewater. The Mohr concentration ratio is 0.7, and the pH of the outflow water is controlled between 9 and 10.6. 如申請專利範圍第1項所述之方法,其中該顆粒床高控制在高於50公分,該過氧化氫相對於含硼廢水中的硼離子的莫爾濃度比為2,該混凝劑中的鈣離子相對於含硼廢水的硼離子的莫爾濃度比為0.7,該出流水酸鹼值控制在9.6。 The method of claim 1, wherein the particle bed height is controlled to be higher than 50 cm, and the molar ratio of the hydrogen peroxide to the boron ion in the boron-containing wastewater is 2, in the coagulant. The Mohr concentration ratio of the calcium ion to the boron ion of the boron-containing wastewater is 0.7, and the pH value of the outflow water is controlled at 9.6. 如申請專利範圍第1項所述之方法,其中該顆粒床高為80公分,該出流水酸鹼值為10。 The method of claim 1, wherein the particle bed has a height of 80 cm and the outlet water has a pH of 10. 如申請專利範圍第1項所述之方法,其中控制含硼廢水的水力滯留時間在18分鐘。 The method of claim 1, wherein the hydraulic retention time of the boron-containing wastewater is controlled to be 18 minutes.
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"以化學過氧沉澱(COP)技術回收含硼酸廢液研究",劉佳勳,國立成功大學碩士論文,2013年 *
"以化學過氧沉澱(COP)技術回收含硼酸廢液研究",劉佳勳,國立成功大學碩士論文,2013年。

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