臺灣博碩士論文加值系統

本研究主要針對醋酸去水之非均勻相共沸蒸餾程序，比較七種醋酸酯類共沸劑，由其中選出最適合本文條件的共沸劑，並由經濟方面探討其最適理由。醋酸為化工上之重要產品用途廣泛，由西元1934年起即有醋酸去水之非均勻相共沸蒸餾程序使用醋酸酯類共沸劑之專利的出現，而在其後更是有大量專利在此一方面。但專利大多表現結果而無詳細過程，本文參照各結果並加以驗證，並提出非均勻相共沸蒸餾塔之設計及求得最適化之操作條件。而在求得最適蒸餾塔後，吾人進一步於動態模擬中測試並找尋一最佳控制架構。

Acetic acid is a very important chemical in industry with wide applications. In various chemical processes, often we need to separate acetic acid and water. This research is to study this important acetic acid dehydration process. Due to tangent pinch characteristics of the process, it is more appropriate to add entrainer and using heterogeneous distillation column for this separation. Seven candidate entrainers will be compared in the thesis and the most economical entrainer for this separation will be recommened. After the entrainer selection, the optimum process design and operating condition will be given. Proper control strategy of this heterogeneous column will also be studied under various feed rate and feed composition changes. Dynamic simulations of various control strategies will be compared.

目 錄
誌謝…………………………………………………………………………….I中文摘要…………….……………………………………………………….II
英文摘要…………………………………………….……...…………….III
目錄………………….………….…………...……………...……………IV
附表目錄………….………………………………………………….………VI
附圖目錄…………………………………………………………………...VII
1 緒論 1
1.1引言….…….………………………….…….…………...………….1
1.2共沸蒸餾之製程目的…………………………………………………3
1.3共沸物之定義及種類……………………………………….……….3
1.4共沸蒸餾製程形式……………………………………………………5
1.5文獻回顧………………………………………………..……………7
1.5.1多重穩態解與參數敏感性……………………...………….7
1.5.2 動態表現與控制……………………………………………11
1.6組織章節…………………………………………………………….11
2 熱力學模式 13
2.1引言…………………………………………………………………..13
2.2模式建立……………………………………………………....……13
2.3熱力數據的收集………………………………………………………14
2.4熱力參數擬合(Regression)…………………………………………14
2.5蒸餘曲線(RCM)…………………………………………………….…24
3共沸劑的選擇和蒸餾塔之設計 27
3.1引言………………………………………………………………..…27
3.2共沸劑的選擇…………………………………………………………27
3.3非均勻相共沸蒸餾塔的設計…………………………………………31
3.4部分水相回流…………………………………………………………42
4動態模擬 45
4.1引言…………………………………………………………….....45
4.2自由度分析……………………………….…………………………45
4.3控制架構……………………………………………………….……48
4.4決定溫度控制板…………………………………………………….49
4.5 控制器參數……………………………………………………………55
4.6單環控制架構……………………………………………………….60
4.7雙環路控制架構…………………………………………………….77
5 結論 86
附錄A熱力學模式……………………………………………………………88
附錄B熱力性質………………………….…………………………………102
附錄C計算TAC使用之公式…………………………………………………107
參考文獻……………………………………………….........….……111
附表目錄
表 2.1 : 熱力模式預測共沸溫度和文獻記載共沸點溫度比較…………16
表 2.2 : 熱力模式預測共沸組成和文獻記載共沸組成比較……………16
表 3.1 : 共沸劑和醋酸價格…….………………………………….....30
表 3.2 : 共沸劑共沸劑好壞比較…………………………………………30
表 3.3 : 初估醋酸-水-醋酸異丁酯蒸餾塔系統之各股組成和流量……38
表 3.4 : 最適化塔設計結果………………………………………………39
表 3.5 : 醋酸乙酯、醋酸異丁酯和醋酸正丁酯之最適化塔的穩態值…41
表 4.1 : 單環路之PI調諧法則……………………………………………55
表 4.2 : 雙環路之PI調諧法則……………………………………………56
表 4.3 : (a)使用第六板作為溫度控制板的單環路控制架構參數(a)使用第二十二板作為溫度控制板的單環路控制架構參數…………………….64
表 4.4 : 雙環路控制架構之控制器參數…………………………………79
附圖目錄
圖 1.1 : 醋酸與水之氣液平衡曲線……………………………………….2
圖 1.2 : 乙醇與水在一大氣壓下溫度與氣-液相組成之關係……………4
圖 1.3 : 丙酮與氯仿在一大氣壓下溫度與氣-液相組成之關係.……….4
圖 1.4 : 丁醇與水在1大氣壓下溫度與汽-液-液相組成之關係…………5
圖 1.5 : 正丁醇去水共沸蒸餾製程示意圖…………………………….…6
圖 1.6 : 以笨為共沸劑次乙醇去水共沸蒸餾製程示意圖………….……6
圖 2.1 : 醋酸乙烯酯(Vinyl acetate)-醋酸(Acetic acid)-水(Water) 之二成分汽液平衡圖和RCM圖..………………………………….........17
圖2.2 : 醋酸乙酯(Ethyl acetate)-醋酸(Acetic acid)-水(Water)之二成分汽液平衡圖和RCM圖……………………..……….....………………18
圖 2.3 : 乙酸正丙酯(n-propyl acetate)-醋酸(Acetic acid)-水(Water)之二成分汽液平衡圖和RCM圖………………….………………….19
圖 2.4 : 乙酸異丙酯(iso-propyl acetate)-醋酸(Acetic acid)-水(Water)之二成分汽液平衡圖和RCM圖……………………………………..20
圖 2.5 : 乙酸正丁酯(n-butyl acetate)-醋酸(Acetic acid)-水(Water)之二成分汽液平衡圖和RCM圖…….…………………………………………21
圖 2.6 : 乙酸異丁酯(iso-butyl acetate)-醋酸(Acetic acid)-水(Water)之二成分汽液平衡圖和RCM圖………………………………………22
圖2.7 : 醋酸正戍酯(N-pentyl acetate)-醋酸(Acetic acid)-水(Water)之二成分汽液平衡圖和RCM圖………………………………………23
圖 2.8 : 計算蒸餘曲線圖所用之簡單批式蒸餾示意圖………………….24
圖 2.9 : 醋酸-水-醋酸乙烯酯蒸餘曲線圖(RCM)…………………………26
圖 3.1 : 醋酸-水-醋酸酯共沸劑非均勻相共沸蒸餾概略圖……..…….29圖 3.2 : 使用醋酸異丁醋平衡曲線，求得塔頂各股流組成………….…36圖 3.3 : 醋酸-水-醋酸異丁酯系統之最適塔板數…………………….…37
圖 3.4 : 乙酸乙酯之進料組成和最小水相回流分率………………….…44
圖 3.5 : 乙酸異丁酯之進料組成和最小水相回流分率………….………44
圖 3.6 : 乙酸正丁酯之進料組成和最小水相回流分率………………….44
圖 4.1 : 二成分蒸餾塔…………………………………………………….46
圖 4.2 : 二成分均勻相共沸蒸餾塔……………………………………….47
圖 4.3 : 二成分非均勻相共沸蒸餾塔…………………………………….47
圖 4.4 : 開環動態階段測試之應答……………………………………...50
圖 4.5 : (a)再沸器熱負載開環干擾測試 +- 0.1 % 之塔板溫度分佈(b)水相回流開環干擾測試 +- 0.1 % 之塔板溫度分佈(c)有機相回流開環干擾測試 +- 0.1 % 之塔板溫度分佈(d)再沸器熱負載、水相回流和有機相回流每一塔板之R值.………………………………………………………..53
圖 4.6 : (a)再沸器熱負載-水相回流量配對之U1、U2圖。(b) 再沸器熱負載-有機相回流量配對之U1、U2圖…………………………………….54
圖 4.7 : 再沸器熱負載開環階梯測試…………………………………….57
圖 4.8 : 水相回流開環階梯測試………………………………………….58
圖 4.9 : 有機回流開環階梯測試…………………….……………………59
圖 4.10 : 單環路控制架構…………………………………………………62
圖 4.11 : 塔板單環路控制架構，進料流量正負20%干擾之動態響應圖.67
圖 4.12 : 塔板單環路控制架構，進料醋酸組成正負20%干擾之動態響應圖……........................................................70
圖 4.13 : 十二塔板單環路控制架構，進料流量正負20%干擾之動態響應圖……........................................................73
圖 4.14 : 十二塔板單環路控制架構，進料醋酸組成正負20%干擾之動態響應圖………………………………………………....................76
圖 4.15 : 雙環路控制架構.……………………………………………….78
圖 4.16 : 控制架構的進料流量干擾正20%……………………………….82
圖 4.17 : 控制架構的進料醋酸姐成干擾正負20%.………………………85

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