臺灣博碩士論文加值系統

有鑑於台灣光電產業發展蓬勃，TFT-LCD蝕刻製程排放高濃度含磷廢液，主要成分包括磷酸、硝酸、醋酸與微量(〈0.5wt%)的鋁、鉬等金屬元素。本研究與廠商合作開發技術以回收及資源化鋁蝕刻廢液。初步測試減壓分餾、真空薄膜蒸餾、低溫結晶及流體化床結晶技術處理廢液。其中真空薄膜蒸餾無法有效分離硝酸、醋酸與磷酸；低溫結晶技術分離金屬離子與磷酸需經過多次再結晶才能純化磷酸，尚有研究空間；而減壓分餾能分離鋁蝕刻廢液中之硝酸；另外，流體化床磷酸鐵結晶技術可藉由化學沉澱於混和酸中產出FePO4·Fe(OH)3之複合物。因此本研究主要針對串聯減壓分餾及流體化床結晶技術回收鋁蝕刻廢液。研究以100 g 鋁蝕刻廢液進行，先以減壓分餾分離鋁蝕刻廢液中之硝酸、醋酸與磷酸，結果顯示將溫度控制為150 oC、真空度為-700 torr時，可分離醋酸(7.49 g)與硝酸(4.81 g)及少量磷酸(5.03 g)至蒸餾端，殘餘液部分則含有磷酸(50.31 g)與鋁、鉬等金屬元素( ~ 0.42 g)；之後利用流體化床反應器處理含磷酸蒸餾液，並回收磷酸鐵結晶。以硫酸鐵為沉澱劑及磷酸亞鐵為晶種，進料之蒸餾液磷酸濃度稀釋至11.6 mM，結果顯示流體化床程序回收廢水磷酸所得磷酸鐵平均粒徑為1 mm，XRD證實其晶相為非晶相，並且處理效果與pH、進料莫耳比等影響磷酸過飽和度之因子有關。控制操作條件為：截面負荷 = 0.688 kg-P m-2 h-1、pHe = 2.30 ± 0.1、Fe/P = 1.2，可達最佳除磷效率為95%，結晶比例為82%。鋁、鉬等殘留在殘餘液之金屬離子則將在後續繼續研究並利用低溫結晶進行分離回收。經過本研究減壓分餾及流體化床串聯技術後，可回收82 %以上之磷酸，而硝酸、醋酸及其他金屬離子待後續以其他技術進行回收處理。

In view of the vigorous development of Taiwan’s optoelectronic industry, the TFT-LCD etching process discharges high-concentration phosphorus-containing wastewater. The main components include phosphoric acid, nitric acid, acetic acid and trace amounts (〈 0.5 wt%) of aluminum, molybdenum and other metal elements. This research is to develop a series of process to recycle and reuse the spent aluminum-etching wastewater. Preliminary tests for vacuum fractional distillation (VFD), vacuum membrane distillation (VMD), melt crystallization (MC) and fluidized-bed crystallization (FBC) to recovery the spent wastewater. Among them, only VFD and FBC could be used to recover phosphoric acid effectively. Therefore, this study mainly focuses on the series of VFD and FBC which was carried out with 100 g of wastewater. Nitric acid and acetic acid were first separate from wastewater by VFD. When the temperature is 150 oC with -700 torr of pressure, acetic acid (7.49 g), nitric acid (4.81 g) and small amount of phosphoric acid (5.03 g) could be separated to the permeate, around 50.31 g of phosphoric acid and metal ions (0.42 g) are remained in residue. Then, use FBC to recover the remaining phosphoric acid from the permeate to produce iron phosphate. When the feed is 11.6 mM-P, the operating conditions were: surface loading = 0.688 kg-Pm-2h-1, pHe = 2.30 ± 0.1, Fe/P = 1.2, the optimum phosphorus removal efficiency was 95 % and the crystallization ratio was 82 %. For the series of VFD and FBC, around 82 % of phosphoric acid can be recovered.

摘要 I
英文延伸摘要 II
誌謝 IX
目錄 XI
表目錄 XIV
圖目錄 XV
第1章 緒論 1
1-1 研究緣起 1
1-2 研究目的與內容 4
第2章 文獻回顧 5
2-1 TFT-LCD產業製程及廢棄物 5
2-1-1 TFT-LCD製程含磷廢液 8
2-2 磷酸鹽的性質 10
2-3 磷的危害及法規標準 12
2-4 鋁蝕刻廢液回收專利 14
2-4-1 磷酸純化再利用方法 [18] 15
2-4-2 一種廢鋁蝕刻液的綜合利用工藝 [19] 17
2-4-3 自鋁蝕刻液中回收硝酸、醋酸或其鹽類的方法 [20] 19
2-5 鋁蝕刻廢液處理技術簡介 20
2-6 分餾技術 22
2-6-1 分餾之原理 22
2-7 薄膜蒸餾技術 25
2-7-1 薄膜蒸餾技術之原理 25
2-7-2 薄膜濕潤 28
2-8 低溫結晶技術 30
2-8-1 低溫結晶技術之原理 30
2-9 流體化床結晶技術 33
2-9-1 流體化床結晶(Fluidized-Bed Crystallization)技術 33
2-9-2 流體化床結晶技術之沿革與發展現況 36
2-9-3 流體化床結晶技術之文獻回顧 38
2-10 晶體之成核 44
2-10-1 結晶與沉澱 44
2-10-2 結晶成長與雙重阻力模式 46
2-10-3 介穩區 48
2-11 磷酸鐵之沉澱化學 51
第3章 實驗設備、材料與方法 53
3-1 研究架構及流程 53
3-2 實驗設備 55
3-2-1 減壓分餾實驗裝置 55
3-2-2 薄膜蒸餾實驗裝置 56
3-2-3 批次化學沉澱實驗裝置 56
3-2-4 流體化床反應器裝置 57
3-2-5 低溫結晶實驗裝置 58
3-3 符號及公式定義 59
3-3-1 減壓分餾之符號及定義 59
3-3-2 真空薄膜蒸餾 59
3-3-3 批次化學沉澱之符號及定義 60
3-3-4 流體化床之符號及定義 61
3-4 實驗藥品 62
3-5 實驗步驟 63
3-5-1 減壓分餾實驗 63
3-5-2 真空薄膜蒸餾 63
3-5-3 批次化學沉澱 64
3-5-4 流體化床 65
3-5-5 低溫結晶 65
3-6 水質監測儀器與分析方法 66
3-6-1 感應耦合電漿園子發射光譜儀（ICP） 66
3-6-2 離子層析儀（IC） 67
3-7 顆粒特性分析 68
3-7-1 X光繞射分析儀 (X-Ray Diffraction analyzer, XRD) 68
3-7-2 掃描式電子顯微鏡（Scanning Electron Microscope，SEM） 68
3-7-3 能量散佈光譜儀（Energy Dispersive Spectrometer，EDS） 69
3-7-4 傅立葉轉換式紅外線光譜儀（Fourier Transform Infrared Spectroscopy, FTIR） 69
3-7-5 熱重分析儀（Thermogravimetric Analyzer, TGA） 69
第4章 結果與討論 70
4-1 技術篩選 71
4-1-1 減壓分餾 71
4-1-2 真空薄膜蒸餾 73
4-1-3 流體化床 77
4-1-3-1 Jar-Test 合成磷酸鐵研究之pHf探討 77
4-1-4 低溫結晶 79
4-2 減壓分餾 82
4-2-1 溫度對分餾之影響 82
4-2-2 真空壓對分餾之影響 85
4-3 流體化床 87
4-3-1 pHe對FBC的影響 89
4-3-2 莫爾比Fe/P對FBC的影響 91
4-3-3 截面負荷對FBC的影響 93
4-3-4 流體化床除磷顆粒表面型態觀察及元素分析 95
4-3-4-1 磷酸鐵顆粒之表面結構與型態 95
4-3-4-2 磷酸鐵顆粒之成分分析 97
4-3-5 流體化床除磷顆粒熱分析 100
4-3-6 流體化床除磷顆粒晶型分析 102
第5章 結論與建議 103
5-1 結論 103
5-1-1 減壓分餾 103
5-1-2 流體化床 103
5-1-2-1 化學混凝磷酸鐵鹽之除磷技術 103
5-1-2-2 流體化床磷酸鐵結晶之除磷技術 104
5-1-3 鋁蝕刻廢液回收之程序 105
5-2 建議 107
參考文獻 108
附錄 A. 利用工業級三價鐵溶液進行流體化床磷酸鐵結晶 113

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