本研究為探討丙烯酸乙酯之合成反應動力與觸媒吸附行為，以一個填充床反應器(PBR)探討丙烯酸乙酯合成的非均相反應動力行為，並選擇以酸性陽離子交換樹脂Amberlyst 35 為觸媒。丙烯酸乙酯合成反應的實驗操作於318.15 K到348.15 K之間，除了改變溫度外，亦探討進料醇/酸莫耳比以及觸媒中的質傳效應。實驗結果顯示酯化反應中，丙烯酸之平衡轉化率隨溫度及醇/酸進料莫耳比的增加而提高；吸附平衡實驗中則發現各成分吸附效應之強弱依序為水>丙烯酸>乙醇>丙烯酸乙酯。動力數據分別以理想擬均相動力模式，非理想擬均相模式，Langmuir-Hinshelwood-Hougen-Waston (LHHW)模式，Eley-Rideal (ER)模式，modified LHHW模式與modified ER模式關聯，並求得最適化的動力參數值，關聯的結果顯示modified LHHW模式為最適合描述丙烯酸乙酯合成反應的非均相催化動力行為。

The heterogeneous kinetics and adsorption behavior for synthesis of ethyl acrylate were investigated with a packed-bed reactor over an acidic cation-exchange resin, Amberlyst 35. The esterification was performed at temperatures from 318.15 K to 348.15 K. In addition to temperature, the effects of molar ratios of alcohol to acid in the feed stream (θB0) and the mass transfer resistance were also studied. The equilibrium conversion of acrylic acid was found to increase with increasing both temperature and the composition of feedθB0. The relative adsorption strengths for the reacting species were determined by adsorption experiments. The results indicated that the magnitude of adsorption strengths followed the order of water > acrylic acid > ethanol > ethyl acrylate. The kinetic data were correlated with the ideal-quasi-homogeneous, the non- ideal-quasi-homogeneous, the Langmuir-Hinshelwood-Hougen-Waston (LHHW), the Eley-Rideal (ER) models, the modified LHHW (M-LHHW) and the modified ER (M-ER). The optimal values of the kinetic parameters were thus determined from the data fitting. The M-LHHW model yielded the best representation for the kinetic behavior of heterogeneous catalytic synthesis of ethyl acrylate.

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).

Altıokka, M. R. and A. ıtak, “ 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).

Blagov, S., S. Parada, O. Bailer, P. Moritz, D. Lam, R. Weinand, and H. Hasse, “ Influence of Ion-Exchange Resin Catalysts on Side Reactions of the Esterification of n-Butanol with Acetic Acid,” Chemical Engineering Science, Vol. 61, pp. 753-765 (2006).

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 (1998).

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).

Gangadwala, J., S. Mankar, S. Mahajani, A. Kienle, and E. Stein, “Esterification of Acetic Acid with Butanol in the Presence of Ion-Exchange Resins as Catalysts,” Ind. Eng. Chem. Res., Vol. 42, pp. 2146-2155 (2003).

Gonzlez, 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).

Grzesik, M., M. Witczak, and J. Skrzypek, “ Kinetics of Ethyl Acrylate Synthesis,” Chemie Ingenieur Tech., Vol. 73, pp. 684 (2001)

Kirbaslar, S. I., H. Z. Terzioglu, and U. Dramur, “ Catalytic Esterification of Methyl Alcohol with Acetic Acid,” Chinese J. Chem. Eng., Vol. 9, pp. 90-96 (2001).

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).

Lee, M. J., P. L. Chou, and H. M. Lin, “ Kinetics of Synthesis and Hydrolysis of Ethyl Benzoate over Amberlyst 39,” Ind. Eng. Chem. Res., Vol. 44, pp. 725-732 (2005).

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).

Lilja, J., J. Aumo, T. Salmi, D. Yu. Murzin, P. Mki-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., J. Wrna, T. Salmi, L. J. Pettersson, J. Ahlkvist, H. Grnman, M. Rnnholm, and D. Yu. Murzin, “ Esterification of Propanoic Acid with Ethanol, 1-Propanol and Butanol over a Heterogeneous Fiber Catalyst,” Chem. Eng. J., Vol. 115, pp. 1-12 (2005).

Lilja, J., D. Yu. Murzin, T. Salmi, J. Aumo, P. Mki-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).

Mki-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).

Malone,. M. F. and M. F. Doherty, “ Finding the Right Angle,” CAST Communication, Vol. 20, pp. 5-12 (1997).

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).

Ppken, T., L. Gtze, 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).

Schwarzer, S. and U. Hoffmann, “ Experimental Reaction Equilibrium and Kinetics of the Liquid-phase Butyl Acrylate Synthesis Applied to Reactive Distillation Simulations,” Chem. Eng. Technol., Vol. 25 , pp. 975-980 (2002).

Selyakova, V. A., G. F. Vytnov, and A. P. Sineokov, “ Study of the Esterification of Acrylic Acid by Butyl Alcohol,” Russ. J. Phys. Chem. (Engl. Transl.), Vol. 50, pp. 1692-1694 (1976).

Seo, Y. and W. H. Hong, “ Kinetics of Esterification of Lactic Acid with Methanol in the Presence of Cation Exchange Resin Using a Pseudo- Homogeneous Model,” J. Chem. Eng. Japan, Vol. 33, pp. 128-133 (2000)

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).

Teo, H. T. R. and B., Saha, “Heterogeneous Catalysed Esterification of Acetic Acid with Isoamyl Alcohol: Kinetic Studies,” Journal of Catalysis, Vol. 228, pp. 174-182 (2004)

Toit, E., R. Schwarzer, and W. Nicol, “Acetone Condensation on a Cation Exchange Resin Catalyst: The Pseudo Equilibrium Phenomenon,” Chemical Engineering Science, Vol. 59, pp. 5545-5550 (2004).

Toukoniitty, B., J.-P. Mikkola, K. Ernen, T. Salmi, and D. Yu Murzin, “Esterification of Propionic Acid under Microwave Irradiation over an Ion-Exchange Resin,” Catalysis Today, Vol. 100, pp. 431-435 (2005).

TRC Thermodynamic Table: Non-Hydrocarbons, Thermodynamic
Research Center, The Texas A & M University System: College Station, TX (1993).

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).

Xu, Z. P. and K. T. Chuang, “Kinetics of Acetic Acid Esterification over Ion Exchange Catalyst,” Cand. J. Chem. Eng., Vol. 74, pp. 493-500 (1996).

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).

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).

Yang, Z., M. Li, and J. Yang, “Kinetics of Esterification of Lactic acid with Ethanol Catalyzed by Cation-Exchange Resins, ” Reactive & Functional Polymers, Vol. 61, pp. 101-114 (2004).

邱如吟，「產製丙酸丁酯之非均相酯化反應研究」，碩士論文，台灣科
技大學化工研究所（2000）。

周珮琳，「苯甲酸乙酯之合成與水解反應動力研究」，碩士論文，台灣科技大學化工研究所（2003）。

廖聖哲，「丙烯酸丁酯合成反應動力研究」，碩士論文，台灣科技大學化工研究所（2005）。

蔡雨廷，「戊二酸與甲醇的非均相酯化反應動力行為研究」，碩士論文，台灣科技大學化工研究所（2005）。

陳昶全，「含水、丙烯酸、醇、丙烯酸酯類混合物之液液相平衡」，碩士論文，台灣科技大學化工研究所（2005）。