臺灣博碩士論文加值系統

本研究以一個固定床反應器探討苯甲酸乙酯合成及水解的非均相反應動力行為，以酸性陽離子交換樹脂Amberlyst 39 為觸媒。苯甲酸乙酯合成反應的實驗操作於323.15 K~353.15 K之間，進料醇/酸莫耳比介於5至9間；水解反應部分的實驗也在323.15 K~353.15 K間進行，酯/水的進料莫耳比介於0.5 ~ 8，醇/水的進料莫耳比介於1 ~ 7.42。
實驗結果顯示酯化反應中，苯甲酸之平衡轉化率隨溫度及醇/酸進料莫耳比的增加而提高。由水解反應的結果發現其不僅反應速率慢，反應轉化率也相當小，當酯/水進料莫耳比4時，在滯留時間約700 (g min / ml )時，水只有約0.2的轉化率；吸附平衡實驗中則發現各成分吸附效應之強弱依序為水>乙醇>苯甲酸乙酯>苯甲酸。
動力數據分別以擬均相動力模式、Langmuir-Hinshelwood、及Eley-Rideal關聯出各模式中的正、逆向碰撞頻率因子、正向活化能、反應熱以及水的吸附平衡吸附常數等；關聯的結果顯示L-H模式為最適合描述苯甲酸乙酯的合成及水解固液催化反應的動力行為。

The kinetic behavior of synthesis and hydrolysis of ethyl benzoate over an acidic cation-exchange resin, Amberlyst 39, was investigated with a fixed-bed reactor. The esterification was peformed at temperatures between 323.15 K and 353.15 K and molar ratios of feed ΘB0 (ethanol to benzoic acid) from 5 to 9. The hydrolysis was conducted also at temperatures between 323.15 K and 353.15 K, and the molar ratios of feed ΘC0´ (ethyl benzoate to water) from 0.5 to 8 and ΘB0 ´ (ethanol to water) from 1 to 7.42.
The equilibrium conversion of benzoic acid was found to increase with increasing both temperature and the composition of feed ΘB0. The results of hydrolysis experiments showed that the reaction rate of hydrolysis was quite slow. Even the molar ratio of feedΘC0´ was as high as about 4, the conversion of water was only about 0.2, while the contact time was as long as 700 (g min/ml ). The relative adsorption strengths for the reacting species were determined from adsorption experiments. The results indicated that the magnitude of adsorption strengths followed the order of water >ethanol >ethyl benzoate > benzoic acid.
The kinetic data were correlated with the quasi-homogeneous, the Langmuir-Hinshelwood, and the Eley-Rideal models. The frequency factor, the activation energy of the forward reactions, the heat of reaction, and the adsorption equilibrium constant of water were determined by correlating the kinetic data with those models. The Langmuir-Hinshelwood model yielded the best representation for the kinetic behavior of liquid-solid catalytic synthesis and hydrolysis of ethyl benzoate.

目 錄
英文摘要 I
中文摘要 II
誌謝 III
目錄 IV
圖表索引 VII
第一章 緒論 1
1-1 前言 1
1-2 文獻回顧 3
1-3 本研究之重點 10
第二章 反應動力及吸附平衡實驗 17
2-1 酯化及水解反應動力數據量測 17
2-2 藥品 19
2-3 實驗步驟 20
2-4 數據處理 22
2-5 動力反應實驗結果 25
2-6 結果與討論 27
2-7 雙成份系統的等溫吸附平衡量測 31
2-8 吸附實驗 34
2-9 實驗步驟 36
2-10 吸附實驗結果 37
2-11 關聯結果 37
第三章 理想溶液擬均相動力模式 54
3-1 動力模式 54
3-2 反應平衡常數計算 55
第四章 非理想溶液動力模式 66
4-1 非理想溶液動力模式 68
4-2 速率常數與吸附常數的訂定 70
4-3 苯甲酸乙酯系統之動力模式關聯結果 73
4-4 質傳阻力之效應 75
4-5 非理想溶液之平衡常數 76
第五章 結論與建議 95
參考文獻 99
符號說明 105

參考文獻
Altıokka, M. R. and A. Çıtak, “Kinetics Study of Esterification of Acetic Acid with Isobutanol in the Presence of Amberlite Catalyst,” Applied Catalysis A: General, Vol. 239, pp. 141-148 (2003).
AL-Jarallah, A. M., M. A. B. Siddiqui, and A. K. K. Lee, "Kinetics of Methyl Tertiary Butyl Ether Synthesis Catalyzed by Ion Exchange
Resin," Cand. J. Chem. Eng., Vol. 66, pp. 802-807 (1988).
Chen, X., Z. Xu, and T. Okuhara, “Liquid Phase Esterification of Acrylic Acid with 1-Butanol Catalyzed by Solid Acid Catalysts,” Applied Catalysis A: General, Vol. 180, pp.261-269 (1999).
Dassy, S., H. Wiame, and F. C. Thyrion, “Kinetics of the Liquid Phase Synthesis and Hydrolysis of Butyl Lactate Catalysed by Cation Exchange Resin,” J. Chem. Tech. Biotechnol., Vol. 59, pp. 149-156 (1994).
Fredenslund, A., J. Gmehling, and P. Rasmussen, “Vapor-Liquid Equilibria Using UNIFAC: A Group-Contribution Method,” Elsevier, Amsterdam (1977).
González, J. C. and J. R. Fair, “Preparation of Tertiary Amyl Alcohol in a Reactive Distillation Column. 1. Reactive Kinetics, Chemical Equilibrium, and Mass-Transfer Issues,” Ind. Eng. Chem. Res., Vol. 36, pp. 3833-3844 (1997).
Hong, G. B., M. J. Lee, and H. M. Lin, “ Vapor-Liquid and Vapor-Liquid-Liquid Equilibria for Mixtures Containing Water, Ethanol, and Ethyl Benzoate,” Ind. Eng. Chem. Res. (accepted).
Lee, M. J., H. T. Wu, and H. M. Lin, “Kinetics of Catalytic Esterification of Acetic Acid and Amyl Alcohol over Dowex,” Ind. Eng. Chem. Res., Vol. 39, pp. 4094-4099 (2000).
Lee, M. J., J. Y. Chiu, and H. M. Lin, “Kinetics of Catalytic Esterification of Acetic Acid and n-Butanol over Amberlyst 35,” Ind. Eng. Chem. Res., Vol. 41, pp. 2882-2887 (2002).
Lilja, J., J. Aumo, T. Salmi, D. Yu. Murzin, P. Mäki-Arvela, M. Sundell, K. Ekman, R. Peltonen, and H. Vainio, “Kinetics of Esterification of Propanoic Acid with Methanol over A Fibrous Polymer-Supported Sulphonic Acid Catalyst,” Applied Catalysis A: General, Vol. 228, pp. 253-267 (2002).
Lilja, J., D. Yu. Murzin, T. Salmi, J. Aumo, P. Mäki-Arvela, and M. Sundell, “Esterification of Different Acids over Heterogeneous and Homogeneous Catalysts and Correlation with Taft Equation,” J. of Molecular Catalysis A: Chem., Vol. 182-183, pp. 555-563 (2002).
Liu, W. T. and C. S. Tan, “Liquid-Phase Esterification of Propionic Acid with n-Butanol,” Ind. Eng. Chem. Res., Vol. 40, pp. 3281-3286 (2001).
Mahajani, S. M., “Reactions of Glyoxylic Acid with Aliphatic Alcohols Using Cationic Exchange Resins as Catalysts,” Reactive & Functional Polymers, Vol. 43, pp. 253-268 (2000).
Mäki-Arvela, P., T. Salmi, M. Sundell, K. Ekman, R. Peltonen, and J. Lehtonen, “Comparison of Polyvinybenzene and Polyolefin Supported Sulphonic Acid Catalysts in the Esterification of Acetic Acid,” Applied Catalysis A: General, Vol.184, pp. 25-32 (1999).
Mazzotti, M., B. Neri, D. Gelosa, A. Kruglov, and M. Morbidelli, "Kinetics of Liquid-Phase Esterification Catalyzed by Acidic Resins," Ind. Eng. Chem. Res., Vol. 36, pp. 3-10 (1997).
National Institute of Standards and Technology (NIST) Chemistry WebBook (http:// webbook.nist.gov/chemistry/).
Pipus, G., I. Plazl, and T. Koloini, “Esterification of Benzoic Acid in Microwave Tubular Flow Reactor,” Chem. Eng. J., Vol. 76, pp. 239-245 (2000).
Pöpken, T., L. Götze, and J. Gmehling, “Reaction Kinetics and Chemical Equilibrium of Homogeneously and Heterogeneously Catalyzed Acetic Acid Esterification with Methanol and Methyl Acetate Hydrolysis,” Ind. Eng. Chem. Res., Vol. 39, pp. 2601-2611 (2000).
Rehfinger, A. and U. Hoffmann, "Kinetics of Methyl Tertiary Butyl Ether Liquid Phase Synthesis Catalyzed by Ion Exchange Resin - I. Intrinsic Rate Expression in Liquid Phase Activities," Chem. Eng. Sci. Vol. 45, pp. 1605-1617 (1990).
Renon, H. and J. M. Prausnitz, “Local Compositions in Thermodynamic Excess Function for Liquid Mixtures,” AIChE J., Vol. 14, pp.135-144 (1968).
Sanz, M. T., R. Murga, and J. L. Cabezas, “Autocatalyzed and Ion-Exchange-Resin-Catalyzed Esterification Kinetics of Lactic Acid with Methanol,” Ind. Eng. Chem. Res., Vol. 41, pp. 512-517 (2002).
Song, W., G. Venimadhavan, J. M. Manning, M. F. Malone, and M. F. Doherty, “ Measurement of Residue Curve Maps and Heterogeneous Kinetics in Methyl Acetate Synthesis,” Ind. Eng. Chem. Res., Vol. 37, pp. 1971-1928 (1998).
Steele, W. V., R. D. Chirico, A. B. Cowell, S. E. Knipmeyer, and A. Nguyen, “ Thermodynamic Properties and Ideal-Gas Enthalpies of Formation for Methyl Benzoate, Ethyl Benzoate, (R)-(+)-Limonene, tert-Amyl Methyl Ether, trans-Crotonaldehyde, and Diethylene Glycol,” J. Chem. Eng. Data, Vol. 47, pp. 667-688 (2002).
Tsao, J. C. Y., T. C. Huang, and H. S. Weng, "Kinetic Studies for the Preparation of Itaconates by Continuous-Flow and Fixed-Bed Methods," Ind. Eng. Chem. Process Des. Dev., Vol. 7, pp. 401-409 (1968).
TRC Thermodynamic table: Non-Hydrocarbons, Thermodynamic Research Center, The Texas A & M University System: College Station, TX (1993).
Xu, X., Y. Zheng, and G. Zheng, "Kinetics and Effectiveness of Catalyst for Synthesis of Methyl tert-Butyl Ether in Catalytic Distillation," Ind. Eng. Chem. Res., Vol. 34, pp. 2232-2236 (1995).
Xu, Z. P. and K. T. Chuang, “Kinetics of Acetic Acid Esterification over Ion Exchange Catalyst,” Canad. J. Chem. Eng., Vol. 74, pp. 493-500 (1996).
Yadav, G. D. and M. B. Thathagar, “Esterification of Maleic Acid with Ethanol over Cation-Exchange Resin Catalysts,” Reactive & Functional Polymers, Vol. 52, pp. 99-110 (2002).
吳瞬膛，「苯甲酸混合物之汽液平衡量測」，碩士論文，台灣科技大學化工研究所（2003）.
洪櫻姿，「含離子溶液混合之固液平衡研究」，碩士論文，台灣科技大學化工研究所（2003）
邱如吟，「產製丙酸丁酯之非均相酯化反應研究」，碩士論文，台灣
技大學化工研究所（2000）.
蔡黛華，「乙醇水溶液在離子交換樹脂的吸附行為研究」碩士論文
台灣科技大學化工研究所（2001）.