臺灣博碩士論文加值系統

本研究介紹反應蒸餾系統產生碳酸二乙酯及甲醇，為碳酸二甲酯
和乙醇的轉酯化反應產物。系統中的動力學模式利用論文(Mueller
and Kenig, 2007) 中所提出的模式，熱力學參數利用ASPEN PLUS 參
數回歸去描述獲得。
本研究中最適化程序設計及操作成本，利用年度總成本(TAC)搜
尋獲得。最適化結果為，操作在乙醇及碳酸二甲酯進料比率為8：1
時，反應蒸餾塔總板數為39 板，碳酸二甲酯進料位置在第29 板，乙
醇進料位置在第9 板時為最適化穩態設計。反應蒸餾塔精餾段出料為
包含甲醇及乙醇的混合流，本研究將分離混合流中的乙醇，由於乙醇
可回收至反應蒸餾塔中再利用。
分離乙醇及甲醇混合流，比較簡單蒸餾塔及萃取蒸餾塔，由結果
可知，簡單蒸餾塔所需要的年度總成本(TAC)，相較於利用間二甲苯
(m-xylene)為萃取劑萃之萃取蒸餾塔要更低。

optimal condition is reached by 8:1 feed
ratio of EtOH : DMC, 39 total trays of distillation column, feed location of dimethyl
carbonate (DMC) at 29th stage and feed location of ethanol (EtOH) at 9th stage. Since
the distillate of the reactive distillation column is a mixture of ethanol and methanol,
further study to separate this mixture is required in order to recover the EtOH for
reaction. Comparison between simple distillation and extractive distillation to separate
EtOH/MeOH mixture was made. Simple distillation was found to have smaller TAC
than the extractive distillation using m-xylene as entrainer.

ACKNOWLEDGEMENT i
ABSTRACT ii
TABLE OF CONTENTS iv
LIST OF FIGURES vi
LIST OF TABLES viii
CHAPTER 1 INTRODUCTION 1
1.1 Background 1
1.2 Literature survey 5
1.2.1 Reactive distillation 5
1.2.2 Diethyl carbonate (DEC) reactive distillation process 6
1.3 Motivation of this work 8
1.4 Organization of this thesis 9
CHAPTER 2 INFORMATION NEEDED IN THE PROCESS SIMULATION
AND ANALYSIS 10
2.1 Adding EMC property into system 10
2.2 Vapor-liquid phase equilibrium 12
2.3 The relative volatility 13
2.4 Material balance line 14
2.5 Kinetic model and parameters 16
2.6 Thermodynamic model 20
Table of contents
v
2.7 Residue curve map (RCM) 27
CHAPTER 3 DESIGN OF DIETHYL CARBONATE VIA REACTIVE
DISTILLATION 33
3.1 Steady state and economic analysis 33
3.2 Process of diethyl carbonate reactive distillation column design 34
3.3 Total annual cost (TAC) for process design optimization 39
3.4 Effect of changing feed locations 50
CHAPTER 4 ETHANOL (EtOH) –METHANOL (MeOH) SEPARATION
SYSTEM 56
4.1 Ethanol (EtOH) - methanol (MeOH) separation system 56
4.2 Simple distillation 59
4.3 Extractive distillation 65
4.3.1 Entrainer selection 67
4.4 Comparison extractive distillation to simple distillation 74
CHAPTER 5 CONCLUSIONS 77
REFERENCES 79
APPENDIX A TAC CALCULATION 82

[1] Buzad, George., and Doherty, M. F., “Design of Three-Component Kinetically
Controlled Reactive Distillation Columns Using Fixed-Point Methods”, Chem.
Eng. Sci., 49, 12, 1947-1963, 1994.
[2] Dunn, B.C., Guenneau, C., Hilton, S.A., Pahnke, J., Eyring, E.M., Dworzanski,
J., Meuzelaar, H.L.C., Hu, J.Z., Solum, M.S., Pugmire, R.J.,“ Production of
Diethyl Carbonate from Ethanol and Carbon Monoxide over a Heterogeneous
Catalyst”, Energy & Fuels, 16, 177-181, 2002.
[3] Georgiadis, M. C., Schenk, M., Pistikopoulos, E. N., and Gani, R., “The
Interactions of Design, Control and Operability in Reactive Distillation
Systems”, Comput. and Chem. Eng., 26, 4, 735-746, 2002.
[4] Gmehling, J., Menke, J, Krafczyk, J., Fischer, K., “Azeotropic Data”, Germany
:Wiley VCH, 2004
[5] Kenig, E. Y., Bäder, H., Górak, A., Beßling, B., Adrian, T., and Shoenmakers,
H., “Investigation of Ethyl Acetate Reactive Distillation Process,” Chem. Eng.
Sci., 56, 6185-6193, 2001.
[6] Lee, J. W., Bruggemann, S., and Marquardt, W., “Shortcut Method for
Kinetically Controlled Reactive Distillation Systems”, AIChE. Journal, 49, 6,
1471-1487, 2003
[7] Luo, H.P. and Xiao, W.D., “A Reactive Distillation Process for a Cascade and
Azeotropic Reaction System: Carbonylation of Ethanol with Dimethyl
Carbonate”, Chem. Eng. Sci., 56, 2001.
[8] Luo, H.P., Xiao W.D, and Zhu K.H., “Isobaric Vapor-Liquid Equilibria of Alkyl
Carbonates with Alcohols,” Fluid Phase Equilibria., 175, 2000.
[9] Ma, X., Fan, M., Zhang, P., “Study on The Catalytic Synthesis of Diethyl
Carbonate from CO and Ethyl Nitrite Over Supported Pd Catalysts”, Catalysis
Communications, 5, 765–770, 2004.
[10] Mahajani, S. M., and Kolah, A. K., “Some Design Aspects of Reactive
80
Distillation Columns (RDC),” Ind. Eng. Chem. Res., 35, 12, 4587-4596, 1996.
[11] Mahajani, S. M., “Design of Reactive Distillation Columns for Multicomponent
Kinetically Controlled Reactive Systems”, Chem. Eng. Sci., 54, 10, 1425-1430,
1999.
[12] Melles, S., Grievink, J., and Schrans, Stany M., “Optimization of the Conceptual
Design of Reactive Distillation Columns,” Chem. Eng. Sci., 55, 11, 2089-2097,
2000.
[13] Mueller, I., and Kenig, E., “Reactive Distillation in a Dividing Wall Column:
Rate-Based Modeling and Simulation”, Ind. End. Chem. Res., 46, 3709-3719,
2007.
[14] Mueller, I., Pech, C., Bhatia, D., Kenig, E.Y., Rate-based Analysis of Reactive
Distillation Sequences with Different Degrees of Integration”, Chem. Eng. Sci.,
62, 7327-7335, 2007.
[15] Noeres, C., Kenig, E.Y., Go´rak, A., “Modelling of Reactive Separation
Processes: Reactive Absorption and Reactive Distillation”, Chemical
Engineering and Processing, 42, 157-178, 2003.
[16] Okasinski, Matthew J., and Doherty, M. F., “Design Method for Kinetically
Controlled, Staged Reactive Distillation Columns”, Ind. Eng. Chem. Res., 37, 7,
2821-2834, 1998.
[17] Okasinski, Matthew, J., and Doherty, M.F., “Thermodynamic Behavior of
Reactive Azeotropes,” AIChE. Journal, 43 (9), 2227-2238, 1997.
[18] Ono, Y. “Dimethyl Carbonate for Environmentally Benign Reactions,”
Pure&Appl. Chem., 68(2), 367-375, 1996.
[19] Paludetto, R., Paret, G.., and Donati, G.., “Multicomponent Distillation with
Chemical Reaction. Mathematical Model Analysis,” Chem. Eng. Sci., 47, 9,
2891-2896, 1992.
[20] Rev, Endre, “Reactive Distillation and Kinetic Azeotropy,” Ind. Eng. Chem.
Res., 33, 9, 2174-2179, 1994.
81
[21] Rodriguez, A., Canosa, J., Dominguez, A., Tojo, J., “Fluid Phase Equilibria”, vol
201, 193-194, 2002.
[22] Rodriguez, A., Canosa, J., Dominguez, A., Tojo, J., “Isobaric Phase Equilibiria
of Diethyl Carbonate with Five Alcohols at 101.3 kPa”, Journal of Chemical and
Engineering Data, 48 (1), 2003.
[23] Roh, N., Dunn, B., Eyring, E.M., Pugmire, R.J., Meuzelaar, H.L.C., “Production
of Diethyl Carbonate from Ethanol and Carbon Monoxide Over a Heterogeneous
Catalytic Flow Reactor”, Fuel Processing Technology, 83, 27-38, 2003.
[24] Seferlis, P., and Grievink, J., “Optimal Design and Sensitivity Analysis of
Reactive Distillation Units Using Collocation Models”, Ind. Eng. Chem. Res.,
40, 7, 1673-1685, 2001.
[25] St´eger, C., Varga, V., Horv´ath, L., R´ev, E., Fony´o, Z., Meyer, M., Lelkes,
Z.,“Feasibility of Extractive Distillation Process Variants in Batch Rectifier
Column”, Chemical Engineering and Processing, 44, 1237-1256, 2005.
[26] Taylor, R., and Krishna, R., “Modelling Reactive Distillation”, Chem. Eng. Sci.,
55, 5183-5229, 2000.
[27] Wang, D., Yang, B., Zhai, X., Zhou, L., “Synthesis of Diethyl Carbonate by
Catalytic Alcoholysis of Urea”, Fuel Processing Technology, 88, 807-812, 2007.
[28] Zeng, K.L., Kuo, C.L., Chien, I.L., “Design and Control of a Reactive
Distillation Column System for The Production of Butyl Acrilate”, Chem. Eng.
Sci. 61, 4417-4431, 2006.