臺灣博碩士論文加值系統

本研究結合廢硫酸、廢硫酸銨液及廢鐵渣三項產業廢棄物，透過酸溶反應及減壓濃縮程序，使結晶溶液達到飽和後，再以批次式結晶程序製成硫酸亞鐵銨結晶顆粒，主要目的是探討結晶應用於跨產業廢棄物資源化技術的可行性，並利用結晶顆粒平衡模式評估結晶成長率的影響因子，包括廢硫酸銨液濃度、亞鐵離子濃度、結晶溶液pH值及結晶時間。
實驗結果顯示，硫酸亞鐵銨結晶產率隨廢硫酸銨液濃度增加而提昇，最高可達88.10 %，廢棄物轉化率可達70.06 %，且結晶效度可達到90 %以上，符合工業生產需求。將硫酸亞鐵銨結晶以XRD分析後，比較JCPDS所訂之硫酸亞鐵銨結晶標準圖譜，結果顯示圖譜峰值範圍相當一致，證實結晶技術應用於跨產業廢棄物資源化相當可行。
結晶成長率是控制結晶產率的關鍵要素，透過顆粒平衡模式可有效評估結晶成長率。實驗結果顯示，當廢硫酸銨液濃度是20 %時，經由顆粒平衡模式所獲得之結晶成長率是1.66×10-3 mm/min，隨著廢硫酸銨液濃度提高至30 %，結晶成長率增至2.19×10-3 mm/min，顯示結晶溶液濃度和結晶成長率呈正比率關係。當結晶溶液pH值介於1~3時，結晶成長率由3.2110-3 mm/min降低至1.6410-3 mm/min，此遞減趨勢顯示pH值應是影響亞鐵離子濃度的主要因素，由實驗得知當亞鐵離子濃度是4.47 M時，溶液的pH=1.87，結晶成長率是2.01×10-3 mm/min，隨著亞鐵離子濃度增至15.21 M，pH值降至1.09，結晶成長率則增加至2.99×10-3 mm/min。當結晶時間從30分鐘增加至120分鐘時，結晶成長率由5.4210-3 mm/min下降至1.1710-3 mm/min，顯示在硫酸亞鐵銨批次結晶程序中，結晶時間對結晶成長率呈反比率關係。
本研究指出廢硫酸、廢硫酸銨液及廢鐵渣三項跨產業廢棄物，可藉由結晶技術資源化，產率亦可達工業化之需求，藉由結晶成長率之影響因子評估結果，得知操控批次式結晶的資源化效率，對結晶技術應用於實務之差距可大幅縮短，是綠色產業科技的重要指引。

This research evaluated the crystal growth rate (CGR) in batch reactor using ferrous (II) ammonium sulfate crystals. The crystals was produced by the recycled industrial wastes including waste sulfuric acid, waste ammonium sulfate, and incinerator slag. The CGR was calculated using standard sieve measurement to obtain crystal size distribution firstly, and then fit into a semi-log plot of the population balance equation. Factors influencing the CGR were investigated including pH values, Fe(II) concentrations, and batch crystallization times. Experimental results showed that as pH=1.0~3.0, the CGR decreased from 3.2110-3 mm/min to 1.6410-3 mm/min, with a lowest CGR=1.5510-3 mm/min at pH=2.5. The pH-depended CGR can be partially attributed to the content of Fe(II) that was oxidized to Fe(III) as pH increased. Additionally, the effect of Fe(II) concentration was verified by comparing pH at 1.09, the CGR=2.9910-3 mm/min for Fe(II) =15.21 M, while pH at 1.87 the CGR decreased to 2.0110-3 mm/min as Fe(II) =4.47 M. A serial of batch crystallization times ranged from 0.5 to 2.0 hrs were tested, and the results showed that CGR decreased from 5.4210-3 mm/min to 1.1710-3 mm/min. This indicated that the lesser the batch crystallization time the higher the CGR, and can be well elucidated via the population balance equation. This study concludes that CGR can be serving as a custom-design process variable, and bridging the gap for crystallization as a viable rematerialization technology to the industrial wastes.

口試委員審定書 I
誌謝 II
中文摘要 III
英文摘要 V
目錄 VI
圖目錄 IX
表目錄 XI
第一章 前言 1
1-1研究背景 1
1-2研究目的 2
1-3研究架構 3
第二章 文獻回顧 4
2-1廢棄物來源及特性 4
2-1-1半導體產業廢硫酸來源 4
2-1-2半導體產業含氨廢液回收程序 5
2-1-3焚化鐵渣處理流程 9
2-2資源化技術 12
2-2-1資源再利用產值 12
2-2-2資源化技術案例 13
2-3結晶 16
2-3-1結晶程序 16
2-3-2結晶的成核及成長 17
2-3-3結晶模式推導 20
2-3-4結晶成長影響因子 24
2-3-5結晶操作形式 30
第三章 研究方法 32
3-1實驗流程 32
3-2實驗藥品與設備 33
3-2-1實驗藥品 33
3-2-2實驗設備 34
3-3實驗方法 37
3-3-1廢硫酸前處理 37
3-3-2廢鐵渣前處理 37
3-3-3廢硫酸銨液前處理 38
3-3-4硫酸亞鐵製備 38
3-3-5廢硫酸銨濃度配製 40
3-3-6硫酸亞鐵銨結晶 40
3-3-7效度測試實驗 41
3-3-8廢棄物轉化率 42
3-3-9 XRD分析 43
3-3-10結晶顆粒之篩分析 44
第四章 結果與討論 45
4-1結晶的資源化技術評估 45
4-1-1硫酸亞鐵銨結晶產率 45
4-1-2廢棄物轉化率 47
4-1-3結晶效度 49
4-1-4結晶XRD分析 50
4-2結晶成長率之探討 51
4-2-1廢硫酸銨液濃度之影響 51
4-2-2結晶溶液pH值之影響 54
4-2-3結晶溶液中亞鐵(II)含量之影響 55
4-2-4結晶時間之影響 56
4-2-5結晶顆粒數量與尺寸之關係 57
4-2-6結晶顆粒之粒徑分布 60
第五章 結論與建議 65
參考文獻 67
附錄一 73

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