臺灣博碩士論文加值系統

本研究探討於製程設計之初步分析時，以平衡反應模式來進行乙酸乙酯反應蒸餾製程模擬之可行性。利用模擬軟體ChemCad，本研究除單一反應蒸餾塔之個別分析，亦考慮串聯汽提塔後之完整製程之影響。
研究分析之項目包括(1)反應蒸餾塔中乙酸/乙醇之進料量比 (2)反應蒸餾塔之精餾段板數 (3)反應蒸餾塔之汽提段板數 (4)反應蒸餾塔之塔底迴流 (5)反應蒸餾塔之塔頂有機迴流 (6)分相槽加水量 (7)氣提塔之迴流等因素。比較採平衡反應模式與反應動力學模式之乙酸乙酯反應蒸餾製程之各項分析，除反應段之影響外，其他製程變數之影響趨勢均相似，差異不大。
綜合分析結果，建議於初步製程評估或設計時，可以採用平衡反應模式來設計反應蒸餾塔。此方法不需詳細之化學動力學與反應蒸餾塔之詳細內部設計資料，可避免耗時費錢之實驗，可以較簡易且迅速的估計並設計出符合產品規格的製程設計條件，如汽提段之板數、精餾段之板數、迴流量之大小等重要變數，而且其數值與採用較複雜之動力學模式設計之結果相當接近。

This work studies the feasibility of using equilibrium model for the preliminary design of the production of ethyl acetate by reactive distillation (RD) process. The commercial simulator ChemCad is used for the analysis of the single reactive distillation column and the whole process.
The effects of design variables include: (1) the feed ratio of RD column (2) the rectifying section in RD column (3) the stripping section in RD column (4) the recycle rate of the bottom product of RD column (5) the organic reflux of RD column (6) the water added in the decanter (7) the recycle of stripper. By comparing the two processes with equilibrium controlled model and kinetic controlled model respectively, the trends of the effects of all variables are similar for these two processes and the deviations are also small.
During the preliminary process design stage, where kinetic data or the column internals are unknown, using the equilibrium mode to design the reactive distillation is suggested. Because it is an economic and efficient way to get reliable design variables.

中文摘要 i
英文摘要 ii
目錄 iii
表目錄 v
圖目錄 vi
第一章 緒論 1
1.1 簡介 1
1.2乙酸乙酯反應蒸餾 3
1.3乙酸乙酯製程之研究 4
1.4研究動機 6
第二章 熱力學與動力學模式 7
2.1 熱力學模式 7
2.1.1 NRTL模式與參數 7
2.1.2 氣液平衡 8
2.1.3 液液平衡 9
2.2 動力學模式 11
第三章 反應蒸餾塔模擬設計 12
3.1 乙酸乙酯製程設計分析 13
3.2 反應蒸餾塔分析 16
3.2.1 乙酸/乙醇進料量之效應 16
3.2.2 精餾段與汽提段之效應 19
3.2.3 塔底迴流分析 20
3.2.4 有機相迴流分析 21
3.3 製程整合分析 27
第四章 乙酸乙酯反應蒸餾反應模式之比較 29
4.1 乙酸乙酯製程概述 29
4.2 反應蒸餾塔分析 31
4.2.1 乙酸/乙醇進料量之效應 31
4.2.2 精餾段與汽提段之效應 33
4.2.3 塔底迴流分析 34
4.2.4 有機相迴流分析 35
4.3 製程整合分析 38
第五章 結論與討論 41
參考文獻 42
表目錄

表2-1 NRTL參數 8
表2-2 乙醇/乙酸乙酯/水系統之共沸點及組成 9
表3-1 進料量之化學計量比 17
表3-2 乙酸乙酯反應蒸餾塔之設計基準 25
表4-1 反應蒸餾塔製程設計基準 38
表4-2 汽提塔與冷凝器耗能比較 39
表4-3 產物比較 39
















圖目錄

圖1-1 反應蒸餾塔 2
圖2-1 乙酸/乙酸乙酯/水之LLE (40℃) 10
圖2-2 乙醇/乙酸乙酯/水之LLE (40℃) 10
圖3-1 第一類型(Type I)之酯化反應蒸餾製程 13
圖3-2 第二類型(Type II)之酯化反應蒸餾製程 14
圖3-3 第三類型(Type III)之酯化反應蒸餾製程 15
圖3-4 反應蒸餾塔 16
圖3-5 乙酸進料量與有機相乙酸乙酯含量之關係 18
圖3-6 乙酸進料量與反應蒸餾塔頂乙酸含量之關係 18
圖3-7 汽提段/精餾段板數與再沸器耗能之關係 19
圖3-8 塔底迴流量與再沸器耗能之關係 20
圖3-9 有機相迴流量與轉化率之關係 21
圖3-10 有機相迴流量與有機相乙酸乙酯濃度之關係 22
圖3-11 有機相迴流量與有機相乙酸濃度之關係 22
圖3-12 有機相迴流量與再沸器耗能之關係 23
圖3-13 反應蒸餾塔內液相濃度(有機相迴流量120kmol/h) 24
圖3-14 反應蒸餾塔內溫度分佈(有機相迴流量120kmol/h) 24
圖3-15 反應蒸餾塔流程圖 26
圖3-16 加水量對於有機迴流量與汽提塔迴流量之關係 27
圖3-17 乙酸乙酯製程流程圖 28
圖4-1 反應模式A之製程流程圖(Tang et al., 2003) 29
圖4-2 反應模式B之製程流程圖 30
圖4-3 乙酸進料量與有機相乙酸乙酯含量之關係 31
圖4-4 乙酸進料量與反應蒸餾塔頂乙酸含量之關係 32
圖4-5 精餾段板數與再沸器耗能之關係 33
圖4-6 塔底迴流量與再沸器耗能之關係 34
圖4-7 有機相迴流量與轉化率之關係 35
圖4-8 有機相迴流量與有機相乙酸濃度之關係 36
圖4-9 有機相迴流量與有機相乙酸乙酯濃度之關係 36
圖4-10 有機相迴流量與再沸器耗能之關係 37
圖4-11 加水量對於有機迴流量之關係 40
圖4-12 加水量對於汽提塔迴流量之關係 40

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