臺灣博碩士論文加值系統

目錄
摘要..............................................................................................................i
Abstract.......................................................................................................ii
目錄............................................................................................................iii
圖目錄 .......................................................................................................vi
表目錄 .......................................................................................................ix
第一章 緒論 .............................................................................................. 1
1.1 前言 ............................................................................................... 1
1.2 背景 ............................................................................................... 2
1.3 文獻回顧....................................................................................... 6
1.4 研究動機與目標 ........................................................................ 10
1.5 章節組織..................................................................................... 11
第二章 甲基丙烯酸甲酯聚合系統熱力學分析 .................................... 12
2.1 前言 ............................................................................................. 12
2.2 甲基丙烯酸甲酯溶液聚合系統成分物性 ................................ 13
2.3 聚合系統POLY-NRTL模型 .................................................... 15
第三章 甲基丙烯酸甲酯溶液聚合反應動力學分析 ............................ 20
3.1 前言 ............................................................................................. 20
3.2 甲基丙烯酸甲酯聚合動力學機制 ............................................ 21
3.2.1 鏈起始反應(Chain initiation) .................................................. 22
3.2.2 鏈增長反應(Chain propagation) ............................................. 22
3.2.3 鏈轉移反應(Chain transfer to monomer and solvent) ............ 22
3.2.4 鏈終止反應(Chain termination) .............................................. 23
3.3 凝膠效應 (Gel effect) ................................................................ 23
3.4 甲基丙烯酸甲酯自由基溶液聚合反應之模擬驗證 ................ 24
第四章 工業級甲基丙烯酸甲酯溶液聚合製程設計模擬與最適化分析 ................................................................................................................... 36
4.1 前言 ............................................................................................. 36
4.2 工業級甲基丙烯酸甲酯溶液聚合文獻製程說明 .................... 37
4.3工業級甲基丙烯酸甲酯溶液聚合製程之年總 成本計算 ............................................................................................ 45
4.4工業級甲基丙烯酸甲酯溶液聚合製程最適化分析 ................. 48
第五章 工業級甲基丙烯酸甲酯溶液聚合製程之動態模擬分析 ........ 58
5.1 前言 ............................................................................................. 58
5.2 控制架構分析 ............................................................................ 58
5.3 進料流量擾動測試(T2塔溫度控制) ........................................ 64
5.3.1 擾動對甲基丙烯酸甲酯-阻聚劑分離塔之影響 .................... 64
5.3.2 擾動對連續式攪拌槽反應器之影響 ..................................... 66
5.3.3 擾動對閃蒸罐之影響 ............................................................. 68
5.3.4 擾動對甲基丙烯酸甲酯回收塔之影響 ................................. 70
5.4 進料流量擾動測試(T2塔組成控制) ........................................ 72
第6章 結論與未來展望 ........................................................................ 75
參考文獻 .................................................................................................. 77
附錄一 TAC計算使用之公式 ............................................................... 79
附錄二 甲基丙烯酸甲酯溶液自由基聚合反應動力式設定資訊 ........ 85


圖目錄
圖1-1 2016年全球前10大聚甲基丙烯酸甲酯輸出國 .......................... 5
圖1-2 全球聚甲基丙烯酸甲酯市場預測 ................................................ 5
圖2-1 甲基丙烯酸甲酯恆壓比熱Aspen模擬結果與實驗值之比較 . 14
圖2-2 乙酸乙酯恆壓比熱Aspen模擬結果與實驗值之比較 ............. 15
圖2-3 MMA/EA之T-xy相圖 ................................................................ 19
圖2-4 MMA/P-HYD之T-xy相圖 ......................................................... 19
圖3-1 Schmidt and Ray(1981)文獻恆溫下不同進料比例之滯留時間vs單體轉化率 .............................................................................................. 29
圖3-2 模擬恆溫下不同進料比例之滯留時間vs單體轉化率 ............ 31
圖3-3凝膠效應因子經調整後模擬恆溫下不同進料比例之滯留時間vs單體轉化率 .......................................................................................... 32
圖3-4 文獻恆溫下不同進料比例之滯留時間vs單體轉化率 ............ 33
圖3-5 文獻不同溫度下同一進料比例之滯留時間vs單體轉化率 .... 33
圖3-6 模擬恆溫下不同進料比例之滯留時間vs單體轉化率 ............ 35
圖3-7 模擬不同溫度下同一進料比例之滯留時間vs單體轉化率 .... 35
圖4-1 甲基丙烯酸甲酯溶液聚合整廠製程之流程圖(mo etal, 2020) . 37
圖4-2 工業級甲基丙烯酸甲酯溶液聚合製程模擬程序圖(串聯) ....... 42
圖4-3 聚合段之聚甲基丙烯酸甲酯之分子量分布圖 .......................... 44
圖4-4 工業級甲基丙烯酸甲酯溶液聚合製程最適化步驟 .................. 50
圖4-5 工業級製程甲基丙烯酸甲酯-阻聚劑分離塔最適化結果 ........ 52
圖4-6 工業級製程連續式攪拌槽反應器最適化結果 .......................... 53
圖4-7 工業級製程甲基丙烯酸甲酯&溶劑回收塔最適化結果 ........... 53
圖4-8 最適化工業級甲基丙烯酸甲酯溶液聚合製程模擬程序圖 ...... 54
圖5-1工業級甲基丙烯酸甲酯溶液聚合製程控制環路(T2塔溫度控制) ............................................................................................................. 62
圖5-2工業級甲基丙烯酸甲酯溶液聚合製程控制環路(T2塔組成控制) ............................................................................................................. 63
圖5-3 甲基丙烯酸甲酯-阻聚劑分離塔之±10%流量擾動變化應答結果(a)T1塔進料流率；(b)T1塔回流槽液位高度；(c)T1塔液槽液位高度；(d)T1塔底阻聚劑組成 .................................................................... 65
圖5-4 連續式攪拌槽反應器之±10%流量擾動變化應答結果(a)連續式攪拌槽反應器液位高度；(b)連續式攪拌反應器溫度 ......................... 67
圖5-5 閃蒸罐之±10%流量擾動變化應答結果(a)閃蒸罐液位高度；(b)閃蒸罐壓力 .............................................................................................. 69
圖5-6 溫度控制下甲基丙烯酸甲酯回收塔之±10%流量擾動變化應答結果(a)T2塔底乙酸乙酯組成；(b)T2塔回流槽液位高度；(c)T2塔液槽高度 ...................................................................................................... 71
圖5-7 甲基丙烯酸甲酯回收塔之±10%流量擾動變化(a)T2塔底乙酸乙酯組成；(b)T2塔回流槽液位高度；(c)T2塔液槽高度 .................. 73


表目錄
表1-1 甲基丙烯酸甲酯聚合製程相關研究歷史表 ................................ 9
表2-1 聚合系統各成分之基本物性比較 .............................................. 13
表2-2 聚合系統POLY-NRTL兩兩成分交互作用參數 ..................... 18
表3-1 甲基丙烯酸甲酯溶液聚合反應機制(Schmidt and Ray, 1981) . 21
表3-2 各文獻使用之進料條件和測試條件 .......................................... 26
表3-3 不同文獻之甲基丙烯酸甲酯溶液聚合動力學速率常數 .......... 27
表4-1 甲基丙烯酸甲酯溶液聚合整廠製程之物流結果 ...................... 37
表4-2 甲基丙烯酸甲酯溶液聚合製程模擬之物流結果(串聯) ........... 43
表4-3 工業級甲基丙烯酸甲酯溶液聚合製程年總成本計算結果 ...... 47
表4-4 最適化甲基丙烯酸甲酯溶液聚合製程模擬之物流結果 .......... 55
表4-5 工業級甲基丙烯酸甲酯溶液聚合製程之基礎案例與最適化結果年總成本比較 ...................................................................................... 56
表5-1 工業級甲基丙烯酸甲酯溶液聚合製程控制器參數 .................. 61
表5-2 甲基丙烯酸甲酯-阻聚劑分離塔在進料流量±10%之擾動排除結果........................................................................................................... 66
表5-3 連續式攪拌槽反應器進料流量±10%之擾動排除結果 ............ 68
表5-4 閃蒸罐在進料流量±10%之擾動排除結果 ................................ 70
表5-5 甲基丙烯酸甲酯回收塔在進料流量±10%之擾動排除結果 .... 72
表5-6 甲基丙烯酸甲酯回收塔進料流量±10%之擾動排除結果 ........ 74

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