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研究生:陳侑利
研究生(外文):Yu-LeeTan
論文名稱:利用流體化床均質顆粒化技術以鐵鹽回收水溶液磷酸之研究
論文名稱(外文):Phosphate Recovery in Fluidized-bed Homogeneous Granulation (FBHG) by using Iron
指導教授:黃耀輝黃耀輝引用關係
指導教授(外文):Yao-Hui Huang
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2014
畢業學年度:102
語文別:中文
論文頁數:109
中文關鍵詞:流體化床顆粒化技術均相成核磷酸回收
外文關鍵詞:Fluidized-bed GranulationHomogenous NucleationPhosphate Recovery
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  • 被引用被引用:1
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有鑑於台灣TFT-LCD廠排放高濃度含磷廢水,本研究利用人工配製模擬之含磷廢水,建立流體化床均質顆粒化技術,以亞鐵回收廢水中之磷酸鹽。
本研究使用Fe^(2+)作為反應的藥劑,先以瓶杯實驗進行化學沉澱實驗,藉由pH值、磷酸初始濃度、雙氧水添加濃度,去了解微溶物系之pH沉澱區間。在瓶杯實驗的基礎上,利用流體化床反應器製造均質顆粒,並以均質顆粒於流體化床中處理濃度為5 mM (150mg-P/L)之含磷溶液,探討pH值、鐵磷進料莫爾、雙氧水濃度及截面積負荷對於回收磷酸的影響。最後,再將流體化床反應器中所產生的均質顆粒取出,進行SEM、EDS、TGA及XRD的檢測。
於雙氧水及亞鐵除磷系統中,在pH值小於4.2的溶液中,添加雙氧水有助於提高亞鐵除磷的效果。在化學沉澱實驗中,pH值會影響除磷的效果。最佳操作pH值=2.5,除磷率為92.84%,磷酸濃度為0.35 mM(11 mg-P/L)。在流體化床除磷實驗中,出流水pH值會影響反應器之截面積負荷極限。最佳操作條件為:截面負荷=0.89 Kg-P/(m2hr)、H2O2/Fe2+進料莫爾比=0.6、pH值= 2.6、Fe/P進料莫爾比= 1.2,去除率可達94.8 %,顆粒化率達85.8 %。流體化床均質顆粒經過6小時鍛燒後,經資料庫比對,發現顆粒為Rodolicoite及Grattarolait晶型的混合物。均質顆粒溶於王水經ICP分析後,確認其Fe/P莫爾比例為1.01。
於亞鐵除磷系統,在化學沉澱實驗中,最佳操作pH值為6.13,此時,除磷率為92.75%,磷酸濃度為0.27mM(8.35 mg-P/L),殘餘溶解性鐵以亞鐵為主。在流體化床除磷實驗中,最佳操作條件為:截面負荷=0.96 Kg-P/(m2 hr)、pH值=5.6、Fe/P=1.5,除磷率為61.1%,顆粒化率為52%。經6小時鍛燒後,經資料庫比對,可得知流體化床均質顆粒為Rodolicoite及Grattarolait晶型之混合物。均質顆粒溶於王水經ICP分析後,確認其Fe/P莫爾比例為1.35。

The objective of this study was to focus on the recovery of phosphorus-containing wastewater from TFT-LCD factory by using Fluidized-bed Homogeneous Granulation Technology. In this study, synthesis phosphorus-containing wastewater was prepared in the laboratory.
In the first stage, ferrous cation was used as the coagulant to carry out the chemical precipitation. The optimal conditions for precipitating the metallic phosphate could be determined by the assessment of experimental parameters, including pH, initial concentration of phosphate hydrogen peroxide. Secondly, on the basis of results in chemical precipitation, parameters of FBHG were designed, including pH of effluent, molar ratio of ferric cation to phosphate, concentration of hydrogen peroxide and cross section loading for determining the optimal operating condition. The pellets from FBHG were determined by SEM, XRD and TGA.
In ferrous and hydrogen peroxide system, removal of phosphate was improved in the presence of hydrogen peroxide. In the chemical precipitation stage, the optimal pH was 2.50 and the phosphate removal was 92.8%. In FBHG stage, for a feed level of 5 mM-P (150 mg-P/L),the optimal parameters were loading =0.89 Kg-P/(m^2∙hr), H2O2/Fe2 molar ratio=0.6, pH_e = 2.6, Fe/P molar ratio= 1.2, 85.8 % of granulation ratio and 94.8 % of removal efficiency were achieved. After annealing, the XRD patterns indicated that pellets from FBHG were composed of the mixtures of Rodolicoite and Grattarolait.
In the chemical precipitation stage of ferrous system, the optimal pH was 6.13 and the phosphate removal was 92.7 %. In FBHG stage, for a feed level of 4 mM-P (120 mg-P/L),the optimal parameters were loading =0.96 Kg-P/(m^2∙hr), pH_e = 5.6, Fe/P molar ratio= 1.5, 52 % of granulation ratio and 61 % of removal efficiency were achieved. After annealing, the XRD patterns indicated that pellets from FBHG composed of the mixtures of Rodolicoite and Grattarolait.

第一章 緒論 1
1-1 研究緣起[1] 1
1-2 研究目的與內容 2
第二章 文獻回顧 3
2-1 TFT-LCD產業製程及廢棄物 3
2-1-1 TFT-LCD製程含磷廢水 5
2-2 磷酸的性質 5
2-3 除磷技術簡介 6
2-4 流體化床結晶技術 9
2-4-1 流體化床操作之原理 9
2-4-2 流體化床結晶技術之原理 9
2-4-3 流體化床結晶技術之沿革與發展現況 11
2-4-4 流體化床結晶技術之文獻回顧 12
2-5 磷酸鹽之沉澱化學 24
2-5-1 磷酸鐵之沉澱曲線 25
2-5-2 氫氧化鐵之沉澱化學 27
2-5-3磷酸亞鐵之沉澱化學 28
2-5-4 氫氧化亞鐵之沉澱化學 29
2-5-5磷酸鋁之沉澱化學 30
2-6 晶體之成核 31
2-6-1 結晶與沉澱 31
2-6-2 成核現象 33
2-6-3 平衡濃度與過飽和度 34
2-6-4 可溶物系與微溶物系之過飽和度定義 35
2-6-5 結晶成長與雙重阻力模式 36
第三章 實驗設備、材料與方法 39
3-1 研究架構及流程 39
3-2 實驗設備 40
3-2-1 批次化學沉澱實驗裝置 40
3-2-2 均質流體化床反應器 40
3-3 符號及公式定義 41
3-3-1 批次化學混凝之符號及定義 41
3-3-2 均質流體化床之符號及定義 42
3-4 實驗藥品 44
3-5 實驗步驟 45
3-5-1 批次混凝實驗 45
3-5-2 均質流體化床實驗 46
3-6 水質監測儀器與分析方法 48
3-6-1 感應耦合電漿原子發射光譜儀 48
3-6-2 分光光度計 49
3-6-3 亞鐵濃度檢定 49
3-6-4 過氧化氫濃度檢定 50
3-7 均質顆粒特性分析 51
3-7-1 掃描式電子顯微鏡 51
3-7-2 能量散佈光譜儀 51
3-7-3 X-ray繞射分析儀 52
3-7-4 熱重分析儀 52
第四章 結果與討論 53
4-1 利用Fe2+與H2O2進行化學沉澱程序除磷 53
4-1-1 Fe2+ 與H2O2莫爾比例的影響 53
4-1-2 pHf的影響 56
4-1-3初始磷酸濃度的影響 58
4-2 利用Fe2+與H2O2進行均質流體化床之除磷技術 60
4-2-1 pHe及Fe/P 進料莫爾比例的影響 60
4-2-2 H2O2/Fe2+進料莫爾比之探討 63
4-2-3截面負荷之探討 66
4-2-4 Al3+的干擾 69
4-2-5 Fe2+與H2O2流體化床除磷均質顆粒表面形態觀察及元素分析 71
4-2-6 Fe2+與H2O2流體化床除磷均質顆粒熱分析 75
4-2-7 Fe2+與H2O2流體化床除磷均質顆粒晶型分析 77
4-3利用Fe2+進行化學沉澱程序除磷 78
4-3-1 pHf的影響 78
4-3-2初始磷酸濃度的影響 81
4-4利用Fe2+進行均質流體化床之除磷技術 83
4-4-1 pHe及Fe/P 進料莫爾比例的影響 83
4-4-2-截面積負荷探討 86
4-4-3 Fe2+流體化床除磷均質顆粒表面形態觀察 89
4-4-4 Fe2+流體化床除磷均質顆粒熱重分析 92
4-4-5 Fe2+流體化床除磷均質顆粒晶型分析 93
第五章 結論與建議 94
5-1 結論 94
5-1-1 Fe2+與H2O2與進行除磷之研究 94
5-1-2 Fe2+進行除磷之研究 95
5-2 建議 96
參考文獻 97
附錄 A 流體化床均質顆粒化技術 101
附錄B 田口實驗設計法用於硫酸鉛流體化床研究 105
附錄C 磷酸鐵FBC除磷之研究 108
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