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研究生:劉文宗
研究生(外文):Liu, Wen-Tzong
論文名稱:酯化反應蒸餾合成丙酸正丁酯研究
論文名稱(外文):Esterification synthesis of n-butyl propionate by reactive distillation
指導教授:談駿嵩談駿嵩引用關係
指導教授(外文):Tan, Chung-Sung
學位類別:博士
校院名稱:國立清華大學
系所名稱:化學工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:176
中文關鍵詞:反應蒸餾催化蒸餾丙酸正丁酯合成強酸型離子交換樹脂觸媒丙酸-丙酸正丁酯汽液平衡酯化反應
外文關鍵詞:Reactive DistillationCatalytic Distillationn-butyl propionate synthesisStrong acidic ion-exchange resin catalystVLE of propionic acid + n-butyl propionateesterfication reaction
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本研究以丙酸正丁酯的酯化反應蒸餾合成為研究載體,結合熱力學和反應動力學的理論,建立完整的基礎數據,探討反應蒸餾的技術細節。具體研究內容包含:
1.從汽液平衡實驗和文獻蒐集得到的數據中,迴歸得到合適的熱力學模式和雙成分參數,以計算酸醇酯水四成分之間的汽液平衡;
2.從商用的固體酸性催化劑中,進行反應實驗,篩選反應速率快,而又適宜放入反應蒸餾塔中的觸媒,計算其反應動力參數,並探討其動力學模式。
3.設計三種不同的觸媒填充方式,以及改變回流比和進料莫耳比等變數進行反應蒸餾實驗。從塔頂、塔底之產物組成和溫度變化情形,驗證反應蒸餾技術可行性和提供製程模擬之參考數據。
4.使用平衡板模式模擬不同變數如回流比變化、進料莫耳比、反應段板數、汽提段板數、精餾段板數等對組成變化的影響,並與實驗結果比較,做為放大設計參考。
主要的研究結果如下:
1.進行丙酸-丙酸正丁酯的汽液平衡實驗,確立NRTL是最合適的熱力學模式,並迴歸雙成分參數。由於丙酸在汽相中的締合現象,汽相的逸度係數必須用化學理論的狀態方程式計算,同時初步證實低壓下的雙重共沸現象。
2.在篩選若干強酸型陽離子交換樹脂後,建議Amberlyst 35 觸媒在兼顧反應活性和物性強度上是較佳的選擇,並獲得其反應動力參數。異相吸附動力的研究顯示,反應的控制步驟是丙酸的被吸附和質子化,然後與液相中的正丁醇反應,反應的機制遵循Eley- Rideal 模式。
3.反應平衡轉化率隨溫度升高而變大。反應為吸熱反應,在80~110℃測得的反應熱為0.46Kcal/mol,從熱力學的角度分析,其值應包含丙酸從締合態解離成單一分子所需的能量。
4.從反應蒸餾實驗和製程模擬中皆顯示,利用反應蒸餾技術可以打破反應平衡,有效提高酯化轉化率,實現單塔製造高純度丙酸正丁酯。而前置反應器的設置,有利於降低反應蒸餾塔的負荷,並保護其內的觸媒,建議應予採用。
5.因丙酸/丙酸正丁酯極難分離,且丙酸具腐蝕性,故理想之製程應使丙酸完全反應,以降低後續分離成本。而完全消耗丙酸的關鍵在於反應段的佈置,包含足夠的觸媒使用量、液體滯留時間、觸媒活性的考量等。
6.在觸媒填充方式的探討中,並流噴射式具有高持液量,汽液分離效率佳,上升的氣體不經過觸媒床降低副反應的發生,是一種不遜於Katapak-S 的新型填充方式。
7.塔底出料獲得高純度丙酸正丁酯(>99.5wt%)是比較經濟可行的作法,而提高丙酸正丁酯純度的主要影響變數為控制塔底溫度,不過要配合反應段良好的設計,以免因汽量大造成分離效率變差和丙酸正丁酯流失太多。
8.採用平衡板模式,配合反應動力式的反應器模式,經過與實驗數據的匹配迴歸得到必要的參數值後,擬合效果相當良好。
本研究所建立的方法和推論結果除了可提供丙酸正丁酯商業化製程設計之外,亦可適用於系統中沸點最高的酯類合成反應蒸餾之用。
The objective of this study was to investigate the reactive distillation technique, a promising technology combining distillation and reaction in one column in order to reduce capital and operating cost, using the esterification of n-butyl propionate from propionic acid and n-butanol as the model system.
The research contents included investigation of chemical equilibrium between each pair in product mixtures and screening of catalysts among the commercial solid acids like acidic exchange resins.
A 50 mm column was used to carry out the catalytic distillation experiments and three kinds of catalysts installation methods were tested. The computer simulation was performed to investigate how the operating variables such as reflux ratio, stripping area, reaction area, rectification area, and boil-up ratio affect the purity of the product and the conversion of propionic acid.
The obtained results of this study are listed as follows:
1.The VLE data of propionic acid + n-butyl propionate were established from the VLE experiments conducted at pressures ranged from 60 kPa~101.3kPa. The NRTL model was found to be the most appropriate to represent liquid phase non-idealities. The Hayden-O’Cornell equation was used to account for vapor phase association. The UNIFAC was found not to describe the VLE because it predicted an azeotrope that was not observed in the experiments. The NRTL-HOC model predicted the existence of a double azeotrope at low pressures that has been reported in the literature.
2.The Amberlyst 35 was observed to possess the highest activity and physical strength among the acidic exchange resins used in the catalyst screening. From the study on chemical reaction kinetics, it was found that the reaction was endothermic with a heat of reaction of 0.46 kcal/mol. Heat due to dissociation of propionic acid was postulated to contribute to the total heat of reaction. The mechanism for this reaction was believed to follow the Eley-Rideal model in which the adsorbed propionic acid reacted with n-butanol in the bulk liquid. The controlling step was the adsorption of propionic acid.
3.N-Propionate with a high purity could be produced from the bottom of a reactive distillation column. The co-jet tray method for the installation of solid catalysts was recommended because of high liquid holdup, low cost, and easy replacement of catalysts.
4.The key to produce n-butyl propionate with a purity of >99.5 wt% was to maintain the bottom temperature of a reactive distillation column sufficiently close to the boiling point of n-butyl propionate. The key to assure a complete conversion of propionic acid in order to prevent from a high separation cost of propionic acid was the setup of a reaction zone, including catalysts amount, liquid holdup, etc. The presence of redundant n-butanol did not result in a higher conversion of propionic acid because it lowered temperature in the reaction zone.
The simulation based on the equilibrium stage model using the Aspen plus simulator was found to correlate the experimental data on temperature profile in column and composition in the bottom and top well. The regressed kinetic parameter could represent both mass transfer and chemical kinetic effects.
摘要 I
目錄 V
表目錄 VIII
圖目錄 XI
第一章 緒 言 1
1-1 前言 1
1-2 文獻回顧 3
1-3 丙酸正丁酯的用途 9
1-4 研究目標和方法 11
第二章 熱力學的探討 13
2-1 前言 13
2-2 汽液平衡資料分析 14
2-3 水-丙酸正丁酯的汽液平衡 15
2-4正丁醇/丙酸正丁酯汽液平衡數據迴歸 16
2-5丙酸-丙酸正丁酯的汽液平衡實驗與迴歸 17
2-6丙酸-丙酸正丁酯雙重共沸點預測 28
2-7 小結 30
第三章 反應動力學探討 32
3-1 前言 32
3-2 羧酸與醇催化酯化反應文獻回顧 32
3-3 觸媒動力實驗 33
3-3-1 原料藥品性質與規格 36
3-3-2 批次反應實驗裝置與步驟 37
3-3-3 不同觸媒反應動力實驗結果 39
3-3-4 反應速率常數計算 45
3-4 異相吸附反應動力 50
3-4-1 模式探討 50
3-4-2 異相催化反應步驟 56
3-5 反應熱的討論 58
3-6 小結 62
第四章 反應蒸餾實驗 64
4-1 前言 64
4-2 反應蒸餾實驗裝置與操作步驟 64
4-3 觸媒裝填方式回顧 68
4-4 反應蒸餾實驗結果 79
4-4-1降液管式 80
4-4-2觸媒網捲式 88
4-4-3 並流噴射板式 94
4-5 水力特性測試 101
4-6 前置反應器實驗結果 104
4-7 小結 107
第五章 反應蒸餾模擬 108
5-1 前言 108
5-2 模式的建立和參數迴歸 109
5-3 塔頂液液分層的考慮 119
5-4 不同變數的影響探討 120
5-4-1 醇酸進料莫耳比之影響 120
5-4-2 回流比之影響 121
5-4-3 精餾段板數之影響 122
5-4-4 萃取段板數之影響 123
5-4-5 反應段板數之影響 124
5-4-6 汽提段板數之影響 125
5-4-7 塔底蒸發比之影響 126
5-4-8 前置反應器反應轉化率之影響 127
5-5 丙酸正丁酯反應蒸餾製程流程 132
5-6 小結 133
第六章 結論 135
參考文獻 137
附錄一 151
附錄二 153
附錄三 154
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