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系統識別號 U0026-0812200915215567
論文名稱(中文) 不同金屬藥劑的流體化床結晶技術處理含磷廢水之研究
論文名稱(英文) Study on Phosphorus Removal by Fluidized-bed Crystallization Technology: Metal Reagent Effect
校院名稱 成功大學
系所名稱(中) 化學工程學系碩博士班
系所名稱(英) Department of Chemical Engineering
學年度 97
學期 2
出版年 98
研究生(中文) 張鈞期
研究生(英文) Chun-chi Chang
電子信箱 n3696117@mail.ncku.edu.tw
學號 n3696117
學位類別 碩士
語文別 中文
論文頁數 118頁
口試委員 口試委員-盧明俊
口試委員-廖志祥
口試委員-王振乾
召集委員-張祖恩
指導教授-黃耀輝
中文關鍵字 回收  成核  流體化床  結晶  除磷  過飽和 
英文關鍵字 Phosphorus recovery  Nucleation  Crystallization  Phosphorus removal  Supersaturation  Fluidized-bed 
學科別分類
中文摘要 本研究以TFT-LCD廠排放之高濃度含磷廢水為目標,利用人工配置之模擬含磷溶液,進行各種可能之磷酸鹽(Ca、Mg、Fe(II、III)、Al)流體化床結晶技術研究。除了大幅將含磷廢水濃度提升至1000 mg-P/L的高負荷,並操作不同進料莫耳比(Me/P)、pH值等變因,找出該技術的最佳操作條件;另針對結晶過程之行為與結晶珠之性質進行深入探討,務求確實評估應用於實廠之可行性。
本研究顯示使用Ca2+、Mg2+、Fe2+等流體化床結晶技術技術適合用來處理低濃(100 mg-P/L)含磷溶液,結晶效率皆可達到70%以上;Fe3+、Al3+等三價金屬鹽,結晶效率亦分別有60%與45%。而使用Ca2+、Fe2+等流體化床結晶技術適合用來處理高濃(1000 mg-P/L)含磷溶液,結晶效率更可達到80%以上;另外,Mg2+、 Fe3+、Al3+等金屬鹽,結晶效率則普遍不理想,主要原因為過飽合度與其他多重干擾影響。此時使用Ca2+之最佳操作條件為:Ca/P=2.0、pHeff=6.0,使用Fe2+之最佳操作條件為:Fe/P=1.2、pHeff=6.0。將以上研究用於處理高濃(1000 mg-P/L)之實廠綜合廢液,去除效果穩定且結晶效率平均可達到70%以上,在實廠應用上具可行性。
磷酸鈣流體化床結晶技術操作過程中,於低過飽和度時,易形成CaHPO4.2H2O的片狀結晶;於高過飽和度時,則易形成Ca5(PO4)3OH的非晶態塊狀成核。而磷酸亞鐵系統中,無論在何種條件(濃度、pH、Fe/P)下,皆易形成Fe3(PO4)2.8H2O的粒狀結晶產物。磷酸鎂、磷酸鐵與磷酸鋁流體化床結晶技術操作過程中,推估主要分別形成Mg3(PO4)2、FePO4.Fe(OH)3、AlPO4.H2O等結晶產物。
英文摘要 The objective of this study is a highly phosphorus concentration of waster water from TFT-LCD factory. All potential phosphate compound (Ca, Mg, Fe(II, III), Al) will be used to treat simulated phosphorus solution by FBC technology. The Concentration of phosphorus will elevate to 1000 mg-P/L in this study. In order to find out the optimum condition of FBC technology, experiments will operate by molar ratio (Me/P) and pH value. Moreover, this study will also discuss in the behavior during crystallization process and the property of crystal pellet. All the trials will evaluate the feasibility in real factory application.
It shows that Ca2+, Mg2+, and Fe2+ FBC technology are suitable to deal with low concentration (100 mg-P/L) phosphorus waste water, and the crystal removal efficiency is over 70%. The crystal removal efficiency of Fe3+ and Al3+ FBC technology is 60% and 45%. Ca2+、Mg2+ FBC technology are suitable to deal with high concentration (1000 mg-P/L) phosphorus waste water, and the crystal removal efficiency is over 80%. The crystal ratio of Mg2+, Fe3+, and Al3+ FBC technology is not good because the effective of supersaturation and others. The optimum condition of Ca2+ system is: Ca/P=2.0, pHeff=6.0, and the optimum condition of Fe2+ system is: Fe/P=1.2, pHeff=6.0. Research in real factory waste water (1000 mg-P/L) is based on previous studies. It demonstrates a stabilize efficiency and the average crystal removal efficiency is over 70%, and its application in real factory is feasible.
During the FBC technology of calcium phosphate operation , CaHPO4.2H2O forms easily in lower saturation and Ca5(PO4)3OH forms easily in higher supersaturation. In addition, the morphology of CaHPO4.2H2O is flake, and Ca5(PO4)3OH is an amorphous type of lump. During the FBC technology of iron (II) phosphate operation, granule of Fe3(PO4)2.8H2O forms in all conditions (concentration, pH, Fe/P). Mg3(PO4)2 , FePO4.Fe(OH)3, and AlPO4.H2O forms during the FBC technology of magnesium phosphate, iron (III) phosphate, and aluminum phosphate operation.
論文目次 摘要 I
Abstract II
誌謝 III
目錄 IV
表目錄 VI
圖目錄 VII
第1章 緒論 1
1-1 研究緣起 1
1-2 研究目的與內容 2
第2章 文獻回顧 3
2-1 磷酸鹽的性質 3
2-2 除磷技術 5
2-3 流體化床結晶技術 6
2-3-1 流體化床結晶技術之沿革與發展現況 6
2-3-2 流體化床結晶除磷技術之文獻回顧 8
2-3-3 流體化床之操作原理 15
2-3-4 流體化床結晶技術之原理 15
2-4 晶體之成核 17
2-4-1 結晶與沉澱 17
2-4-2 成核現象 19
2-4-3 結晶成長與雙重阻力模式 20
2-4-4 平衡濃度與過飽合 22
2-4-5 介穩區 24
2-5 磷酸鹽之沉澱化學 27
2-5-1 磷酸鈣之沉澱化學 28
2-5-2 磷酸鎂之沉澱化學 31
2-5-3 磷酸亞鐵之沉澱化學 32
2-5-4 磷酸鐵之沉澱化學 33
2-5-5 磷酸鋁之沉澱化學 34
第3章 實驗設備、材料與方法 35
3-1 研究架構及流程 35
3-2 流體化床結晶實驗 36
3-2-1 實驗設備 36
3-2-2 實驗藥品 38
3-2-3 實驗步驟 38
3-3 水樣分析方法 40
3-4 結晶珠特性分析 41
3-4-1 SEM表面型態觀察 41
3-4-2 EDS元素分析 43
3-4-3 XRD晶相分析 44

第4章 結果與討論 46
4-1 磷酸鈣—流體化床結晶 46
4-1-1 磷酸鈣—最佳操作條件的取得 46
4-1-2 磷酸鈣—結晶珠表面型態觀察 52
4-1-3 磷酸鈣—結晶珠元素分析 56
4-1-3 磷酸鈣—結晶珠晶相分析 56
4-2 磷酸鎂—流體化床結晶 59
4-2-1 磷酸鎂—最佳操作條件的取得 59
4-2-2 磷酸鎂—結晶珠表面型態觀察 65
4-2-3 磷酸鎂—結晶珠元素分析 67
4-2-4 磷酸鎂—結晶珠晶相分析 67
4-3 磷酸亞鐵—流體化床結晶 69
4-3-1 磷酸亞鐵—最佳操作條件的取得 69
4-3-2 磷酸亞鐵—結晶珠表面型態觀察 74
4-3-3 磷酸亞鐵—結晶珠元素分析 75
4-3-4 磷酸亞鐵—結晶珠晶相分析 75
4-4 磷酸鐵—流體化床結晶 77
4-4-1 磷酸鐵—最佳操作條件的取得 77
4-4-2 磷酸鐵—結晶珠表面型態觀察 82
4-4-3 磷酸鐵—結晶珠元素分析 83
4-4-4 磷酸鐵—結晶珠晶相分析 83
4-5 磷酸鋁—流體化床結晶 84
4-5-1 磷酸鋁—最佳操作條件的取得 84
4-5-2 磷酸鋁—結晶珠表面型態觀察 89
4-5-3 磷酸鋁—結晶珠元素分析 90
4-5-4 磷酸鋁—結晶珠晶相分析 90
4-6 各種磷酸鹽流體化床結晶之整體效益評估 91
4-7 實廠綜合廢水研究 93
4-7-1 磷酸鈣—流體化床結晶 93
4-7-2 磷酸亞鐵—流體化床結晶 94
4-7-3 實廠廢水整體效益評估 95
第5章 結論與建議 96
5-1 結論 96
5-2 建議 97
參考文獻 98
附錄A-水力條件之設計 102
附錄B-結晶珠元素分析 108
附錄C-流體化床均相成核結晶技術 116
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