臺灣博碩士論文加值系統

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

1.Abrams, D.S.; Prausnitz, J.M. “Statistical thermodynamics of liquid mixtures: A new expression for the excess Gibbs energy of partly or completely miscible systems”, AIChE J., 21, 116-128 (1975).
2.Adams, J.R.; Smith, Jr., L.A.; Hearn, D.; Jones, Jr., E.M.; Arganbright, R.P. “Integrated process for the production of TAME”, US Patent 5,792,891 (1998).
3.Agreda,V.H., “Reactive distillation process for the production of methyl acetate”, US Patent 4,435,595 (1984).
4.Agreda, V.H., Parin, L.R., and Heise, W.H. “High-purity methylacetate via reactive distillation”, Chem. Eng. Prog., 86(2), 40 (1990).
5.Amer Amezaga, S. AN. QUIM., 71, 127 (1975a).
6.Amer Amezaga, S. AN. QUIM., 71, 117 (1975b).
7.Andrianova, T.I., Kinet. Katal., 5, 927 (1964).
8.Aspen Technology Inc., ASPEN PLUS, User Guide, Release 10: Cambridge, MA, USA (1998).
9.Backhaus, A. A. “Continuous processes for the manufacture of esters”, US Patent 1,400,849 (1921).
10.Bamum, C.; Blaisdell C.T. “Reactive distillation process for free radical halogenation” US Patent 5,449,801 (1995).
11.Bart, H.J.; Reidetschlager, J.; Schatka, K.; Lehmann, A. “Kinetics of esterification of levulinic acid with n-butanol by homogeneous catalysis”, Ind. Eng. Chem. Res.,, 33(1), 21-25 (1994).
12.Bart, H.J.; Kaltenbruuner, W.; Landschutzer, H. “Kinetics of esterification of acetic acid with propyl alcohol by heterogeneous catalysis”, Intl. J. Chem. Kinet., 28, 649 (1996).
13.Baur, R.; Higler, A.P.; Taylor, R.; Krishna, R. “Comparison of equilibrium stage and nonequilibrium stage models for reactive distillation”, Chemical Engineering J., 76, 33—47 (2000).
14.Baur, R.; Taylor, R.; Krishna, R. “Influence of column hardware on the performance of reactive distillation columns”, Catalysis Today, 66(2-4), 225-232 (2001).
15.Berman, S., Isbenjian, H., and Othmer, F. “Esterification: continuous production of dibutyl phthalate in a distillation column”, Ind. Eng. Chem., 40(11), 2139 (1948).
16.Berrod, G., Grillon E.; Klinger F. “Hydrolysis of alkyl dicarboxylates”, European Patent 571,299 (1993).
17.Berteau, P.; Ceckiewicz, S.; Delmon, B. “Role of the acid-base properties of aluminas, modified g-alumina, and silica-alumina in 1-butanol dehydration”, Applied Catalysis, 31(2), 361-383 (1987).
18.Bessling, B.; Loning, J.M.; Ohligschlager, A.; Schembecker, G.; Sundmacher, K. “Investigations on the synthesis of methyl acetate in a heterogeneous reactive distillation process”, Chemical Engineering & Technology, 21(5), 393-400 (1998).
19.Burguet M.C.; Monton, J. B.; Munoz, R.; Wisniak, J.; Segura, H. “Polyazeotropy in associating systems: the 2-methylpropyl ethanoate + ethanoic acid system”, J. Chem. Eng. Data, 41(5), 1191-1195 (1996).
20.Chakrabarti, A.; Sharma, M.M. “Cationic ion exchange resins as catalyst” Reactive Polymers , 20(1-2), 1-45 (1993).
21.Chen, J. “Process for the production of alkyl benzene”, US Patent 5,866,736 (1999).
22.Chodorge J.A.; Cosyns J.; Dorbon M.; Didillon B.; Viltard J. “Process for the production of high purity isobutene combining reactive distillation with hydroisomerisation and skeletal isomerisation”, European Patent 850,903 (1998).
23.Chopade, S.P.; Sharma, M. M. “Acetalization of ethylene glycol with formaldehyde using cation-exchange resins as catalysts: batch versus reactive distillation”, Reactive and Functional Polymers, 34(1), 37-45 (1997).
24.Christensen, S.; Olson, J. “Phase equilibria and multi azeotrope of the acetic acid-isobutyl acetate”, Fluid Phase Equilib., 79, 187-199 (1992).
25.Chu S.J.; Chen. Y.W. “Shape-selective alkylation of naphthalene with isopropanol over large zeolites”, Applied Catalysis A.: General, 123, 51-58 (1995).
26.Corma, A.; Garcia H.; Iborra S. “Modified faujasite zeolites as catalysts in organic reactions: esterification of carboxylic acid in the presence of hy zeolites”, J. of Catalysis, 120, 78-87 (1989).
27.Davies, D.; Jenkins, J.D.; Dilfanian, S. ”Distillation with chemical reaction - the distillation of formaldehyde solutions in a sieve plate colomn”, IChemE Symp Series, 56, 4.2/65 (1975).
28.De Bruin, P.R.; Law, J.S.; Vriens, V.A. “Method and apparatus for the continuous production of diaryl carbonates”, US Patent 6,294,684 (2001).
29.DeGarmo, J.L.; Parulekar, V.N.; Pinjala, V. “Consider reactive distillation”, Chem. Eng. Pro., 3, 43-50 (1992).
30.DIPPR, Data Compilation of Pure Compound Properties, National Institute of Science and Technology; Standard Reference Data: Gaithersburg, MD (1995).
31.Doherty, M.F.; Buzard G. “Reactive distillation by design”, Supplement to The Chemical Engineer, 27 Aug., 7 (1992).
32.Domingos, B.; Doherty, M.F. “Design and minimum-reflux calculations for double-feed multicomponent reactive distillation columns”, Chem. Eng. Sci., 43(9), 2377-2389 (1988).
33.Dorai S. “Alkanolysis of polyether polyol esters by reactive distillation”, WO Patent 9,723,559 (1997).
34.Doughty A.; Townsend P. “Catalytic distillation oligomerization of vinyl monomers to make polymerizable vinyl monomer oligomers uses thereof and methods for same”, US Patent 6,004,256 (1999).
35.Drinkard W.C.; Grunewald G.C.; Reimer R.A. “Production of cyclohexyladipates and adipic acid”, European Patent 748,309 (1995).
36.Flato J. and Hoffmann U. “Development and start-up of a fixed bed reaction column for manufacturing antiknock enhancer MTBE”, Chemical Engineering Technology,15(3), 193-201 (1992).
37.Flick, K.; Erdbrugger; C.F.; Brocker, F.J.; Meyer, G.; Schwab, E.; Herion, C. “Hydrogenation process”, US Patent 5,866,734 (1999).
38.Ellenberger, J.; Krishna, R. “Counter-current operation of structured catalytically packed distillation columns: Pressure drop, hold-up and mixing”, Chem. Eng. Sci., 54, 1339-1345 (1999).
39.Fredenslund, A.; Jones, R.L.; Prausnitz, J.M. “Group-contribution estimation of activity coefficients in nonideal liquid mixtures”, AIChE J., 21, 1086-1098 (1975).
40.Frey S.J. “Paraffin treating process for mercaptan and olefin removal”, US Patent 5,463,134 (1995).
41.Fuchigami, Y. “Hydrolysis of methyl acetate in distillation column packed with reactive packing of ion exchange resin”, J. Chem. Eng. Japan, 23(3), 354-359 (1990).
42.Gaspillo, P.D.; Abella, L.C.; Goto, S. “Dehydrogenation of 2-propanol in reactive distillation column for chemical heat pump”, J. Chem. Eng. Japan, 31(3), 440-444 (1998).
43.Gaw, W.J.; Swinton, F.L. “Thermodynamic properties of binary systems containing hexafluorobenzene. Part 4.-Excess Gibbs free energies of the three systems hexafluorobenzene + benzene, toluene, and p-xylene”, Trans. Faraday Soc., 64, 2023-2034 (1968).
44.Gentry, J., “Catalytic distillation to produce orthoxilene and paraxilene”, US Patent 5,516,955 (1996).
45.Gildert, G.R. “Hydrogenation of benzene to cyclohexane”, US Patent, 6,187,980 (2001).
46.Gimenez, J.; Costa, J.; Cervera-March, S. ”Catalysis by ion-exchange sulfonation resins: comparative study of gel and marcroporous types and influence of divinylbenzene concentration”, Applied Catalysis, 31, 221-234 (1987).
47.Gmehling, J.; Onken, U. “Vapor-Liquid Equilibrium Data Collection, Chemistry Data Series”, DECHEMA: Frankfurt, Germany (1977a).
48.Gmehling, J.; Onken, U. “Liquid-Liquid Equilibrium Data Collection, Chemistry Data Series” DECHEMA: Frankfurt, Germany (1977b).
49.Gonzalez, E.; Ortega, J. “Densities and isobaric vapor-liquid equilibria for the mixtures formed by four butyl esters and 1-butanol”, J. Chem. Eng. Data, 41, 53-58 (1996).
50.Gonzalez, J.C., Fair J.R. “Preparation of tertiary amyl alcohol in a reactive distillation column. 1. Reaction kinetics, chemical equilibrium and mass transfer issues”, Ind. Eng. Chem. Res., 36(9), 3833 (1977).
51.Gonzalez, J.C., Subawalla, H., Fair, J.R. “Preparation of'' tertiary amyl alcohol in a reactive distillation column. 2. Experimental demonstration and simulation of the column”, Ind. Eng. Chem. Res., 36(9), 3845 (1997).
52.Götze, L.; Bailer, O.; Moritz, P.; von Scala, C. “Reactive distillation with KATAPAK®”, Catalysis Today, 69(1-4), 201-208 (2001).
53.Gu J.; Fang Y.; Jiang G. “Technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation”, CN 1,180,692 (1998).
54.Hamilton D.M. “Process for catalytic hydroxylation of benzene”, US Patent 2001,044,559 (2001).
55.Hamilton D.M.; Murray B. D. “Process for catalytic hydroxylation of, saturated or unsaturated, aliphatic compounds”, US Patent 2002,002,312 (2002).
56.Hammershaimb H.U.; Vora B.V. “Oligomer production with catalytic distillation”, US Patent 6,025,533 (2000).
57.Han, S.J.; Jin, Y.; Yu, Z.Q “Application of a fluidized reaction-distillation column for hydrolysis of methyl acetate”, Chemical Engineering J., 66, 227-230 (1997).
58.Hanika, J.; Kolena, J.; Smejkal, Q. “Butylacetate via reactive distillation - modelling and experiment”, Chem. Eng. Sci., 54(21), 5205-5209 (1999).
59.Hanika, J.; Smejkal, Q.;Kolena, J. “2-Methylpropylacetate synthesis via catalytic distillation”, Catalysis Today, 66(2-4), 219-223 (2001).
60.Hawes, R.W.; Kabel R.L. “Thermodynamic equilibrium in the vapor phase esterification of acetic acid with ethanol”, AIChE J., 14(4), 606-611 (1968).
61.Hayden, J.G.; O’Connell, J.P. “A generalized method for predicting second virial coefficients”, Ind. Eng. Chem. Process Des. Dev., 14(3), 209-216 (1975) .
62.Hearn, D.; Putman, H.M. “Hydrodesulfurization process utilizing a distillation column reactor”, US Patent 5,779,883 (1998).
63.Hearn, D.; Arganbright, R.P.; Smith, Jr., L.A.; Adams, J.R. “Process for alkylation of benzene”, US Patent 5,894,076 (1999).
64.Hessel D., Phys. Chem., 229, 199 (1965).
65.Hickey, T.P.; Hearn, D.; Putman, H.M. “Hydroconversion process”, US Patent 5,961,815 (1999).
66.Higler, A.P.; Taylor, R.; Krishna, R. “Modeling of a reactive separation process using a nonequilibrium stage model”, Computers Chem. Engng., 22, suppl., s111-s118 (1998).
67.Higler, A.P.; Krishna, R.; Ellenberger, J.; Taylor, R. “Counter-current operation of a structured catalytically packed bed reactor: Liquid-phase mixing and mass transfer”, Chem. Eng. Sci., 54, 5145-5152 (1999).
68.Hildreth J.M. “Removal of alpha-methyl styrene from cumene”, US Patent 5,905,178 (1999).
69.Hofman, T.; Nagata, I. “Determinztion of association constants for alcohols based on ethers as homomorphs”, Fluid Phase Equilib., 25, 113-128 (1986).
70.Horseley, L.H. “Azeotropic data-III”, Advances in Chemistry Series 116; American Chemical Society: Washington, DC (1973).
71.Huang, C.; Ng, F.T.T.; Rempel, G.L. “Application of catalytic distillation for the aldol condensation of acetone: The effect of the mass transfer and kinetic rates on the yield and selectivity”, Chem. Eng. Sci., 55, 5919-5931 (2000).
72.Huff, Jr., G.A.; Owen, O.S.; Alexander, B.D.; Rundell, D.N.; Reagan, W.J.; Yoo, J.S. “Sulfur removal by catalytic distillation”, US Patent 5,863,419 (1999).
73.Indu, B.; Ernst, W.R.; Gelbaun, L.T. “Methanol-formic esterification equilibrium in sulfuric acid”, Ind. Eng. Chem. Res., 32, 981-985 (1993).
74.Jayadeokar, S.S., Sharma, S.S. “Simultaneous hydration and etherification of isoamylene using sub-azeotropic ethanol: Use of Ion Exchange resins as catalysts”, Reactive Polymers, 19, 169-179 (1993).
75.Jiang, Z.; Wang, Y. “Preparation of dimethyl carbonate through transesterification in a catalytic distillation column”, Huaxue Gongcheng(China), 29(3), 29-32 (2001).
76.Jones E.M Jr. “Catalytic distillation reactor”, US Patent 5,130,102 (1992).
77.Kampmann, D.; Stuhlmuller, G. “Process for the continuous preparation of 2,2,6,6-tetramethylpiridine”, US Patent 5,663,351 (1997).
78.Kang, Y.W.; Lee, Y.Y.; Lee, W.K. “Vapor-liquid equilibria with chemical reaction equilibrium- Systems containing acetic acid, ethyl alcohol, water, and ethyl acetate”, J. Chem. Eng. Japan, 25(6), 649 —655 (1982).
79.Kenig, E. Y.; Bader, H.; Goraka, A.; Bebling, B.; Adrian, T. ; Schoenmakers, H. “Investigation of ethyl acetate reactive distillation process”, Chem. Eng. Sci., 56, 6185—6193 (2001).
80.Knifton, J.F.; Sanderson, J.R.; Stockton, M.E. ”Use of reactive distillation in the dehydration of tertiary butyl alcohol”, US Patent 5,811,620 (1998).
81.Kolodziej, A.; Jaroszynski, M.; Hoffmann, A.; Górak, A. ”Determination of catalytic packing characteristics for reactive distillation”, Catalysis Today, 69(1-4), 75-85 (2001).
82.Krishnaiah, D.; Rao, M.B. Indian J. of Technology, 22, 268 (1984).
83.Kreul, L.U.; Gorak, A.; Dittrich, C.; Barton T.I. “Dynamic catalytic distillation: advanced simulation and experimental validation”, Computers Chem. Engng., 22, suppl., s371-s378 (1998).
84.Kumar, A.; Daoutidis, P. ”Modeling, analysis and control of ethylene glycol reactive distillation column”, AIChE J., 45(1), 51-68 (1999).
85.Kunz, U.; Hoffmann, U. “Preparation of catalytic polymer/ceramic ion exchange packings for reactive distillation columns”, 6th Int. Symp. Scientific Basis for the Preparation of Het. Catalysts, Sep.6.-., Louvain-La-neuve, Belgium (1994).
86.Kushner, T.M.; Shutova, G.V.; Raeva, V. M.; Serafimov, L. A. “Biazeotropy in the propionic acid-butyl propionate system”, Russian J. of Phys. Chem., 66, 445-447 (1992).
87.Ladish, M.R.; Hendrickson, R.L.; Brewer, M.A.; Westgate, P.J. “Catalyst-induced yield ebhancement in a tubular reactor”, Ind. Eng. Chem. Res., 32, 1888-1894 (1993).
88.Lawson, K.H.; Nkosi, B. ”Production of MIBK using catalytic distillation technology”, US Patent 6,008,416 (1999).
89.Lee, J.-H.; Dudukovic, M.P. “Comparison of the equilibrium and nonequilibrium models for a multicomponent reactive distillation column”, Computers Chem. Engng., 23(1), 159-172 (1998).
90.Lee, M.-J.; Wu, H.-T.; Kang, C.-H.; Lin, H.-M. “Kinetic behavior of amyl acetate synthesis catalyzed by acidic cation exchange resin”, J. Chin. Inst. Chem. Engrs., 30, 117 (1999).
91.Lee, M.-J.; Wu, H.-T.; Kang, C.-H.; Lin, H.-M. “Kinetics of catalytic esterification of acetic acid and amyl alcohol over Dowex”, Ind. Eng. Chem. Res., 39(11), 4094-4099 (2000).
92.Leu, A.D.; Robinson, D.B. “Vapor-liquid equilibrium in selected binary systems of interest to the chemical industry. in experimental results for phase equilibria and pure component properties”, DIPPR Data Series 1, J.R. Cunningham, D.K. Johns eds. DIPPR: New York (1991).
93.Lilja J.; Aumo J.; Salmi T.; Murzin D.Y.; Maki-Arvela P.; Sundell M.; Ekman K.; Peltonen R.; Vainio H. “Kinetics of esterification of propanoic acid with methanol over a fibrous polymer-supported sulphonic acid catalys”, Applied Catalysis A: General, 228(1), 253-267 (2002).
94.Lloyd, L.; Wyatt P.A.H. “The vapour pressures of nitric acid solutions. Part I. New azeotropes in the water-dinitrogen pentaoxide system”, J. Chem. Soc., 2249-2252 (1955).
95.Luo, H.P.; Xiao, W.D. "A reactive distillation process for a cascade and azeotropic reaction system: Carbonylation of ethanol with dimethyl carbonate", Chem. Eng. Sci., 56(2), 403-410 (2001).
96.Ma,Y.; Wang, Q.L.; Hao, Y.; Ji, X.; Qiu Q. “Zeolite-catalyzed esterification. i. synthesis of acetates, benzoates and phthalates”, Applied Catalysis A: General, 139, 51-57 (1996).
97.Marek, J. “Rectification with chemical reaction. II. Plant rectification of a water-acetic acid-acetic anhydride mixtuure”, Coll. Czech. Chem. Commun., 21, 1560 (1956).
98.Marker, T.L.; Funk, G.A.; Barger, P.T.; Hammershaimb, H.U. “Two-stage process for producing diisopropyl ether using catalytic distillation”, US Patent 5,744,645 (1998).
99.Masamoto J.; Matsuzaki K. “Development of methylal synthesis by reactive distillation”, J. Chem. Eng. Japan, 27(1), 1 (1994).
100.Matouq M., Quitain, A.T., Takahashi, K., and Goto, S., “Reactive distillation for synthesizing of ETBE from low grade alcohol catalyzed by potassium hydrogen sulfate”, Ind. Eng. Chem. Res., 35, 982 (1996).
101.Mazzotti, M.; Neri, B.; Gelosa, D.; Kruglov, A.; Morbidelli, M. “Kinetics of liquid-phase esterification catalyzed by acidic resins”, Ind. Eng. Chem. Res., 36, 3 (1997).
102.Miracca, I.; Tagliabue, L.; Trotta, R. “Multitubular reactors for etherifications”, Chem. Eng. Sci., 51(10), 2349-2358 (1996).
103.Mokhtarzadeh, M.; Murray, R.E., “Transvinylation process by reactive distillation”, US Patent 5,210,207 (1993).
104.Mori, T.; Fujita, K.; Kajita, Y.; Takai, M. ”Method for producing a dimerized aldehyde” US Patent 5,667,644 (1994).
105.Moritz, P.; Hasse, H. “Fluid dynamics in reactive distillation packing Katapakt-S”. Chem. Eng. Sci., 54, 1367-1374 (1999).
106.Murphree, B.; Ozer, R. ”Preparation of pentenoic acid”, US Patent 5,536,873 (1996).
107.Nemphos S.P.; Hearn D. ”Amination process”, US Patent 5,679,862 (1997).
108.Neumann, R.; Sasson Y. “Recovery of dilute acetic acid by esterification in a packed chemorectification column”, Ind. Eng. Chem. Process Des. Dev., 23(4), 854-859 (1984).
109.Okasinski, M.J.; Doherty, M.F. “Prediction of heterogeneous reactive azeotropes in esterification systems”, Chem. Eng. Sci., 55(22), 5263-5271 (2000).
110.Okur, H.; Bayramoglu, M. ”The effect of the liquid-phase activity model on the simulation of ethyl acetate production by reactive distillation”, Ind. Eng. Chem. Res., 40(16), 3639-3646 (2001).
111.Oudshoorn, O.L.; Janissen, M.; van Kooten, W.E.J.; Jansen, J.C.; van Bekkum, H.; van den Bleek, C.M.; Calis, H.P.A. “Novel structured catalyst packing for catalytic distillation of ETBE”, Chem. Eng. Sci., 54(10), 1413-1418, (1999).
112.Pipus, G.; Plazl, I.; Koloini, T. ”Esterification of benzoic acid in microwave tubular flow reactor”, Chemical Engineering J., 76(3), 239-245 (2000).
113.Podrebarac, G.G.; Ng, F.T.T.; Rempel, G.L ”The production of diacetone alcohol with catalytic distillation. Part I: Catalytic distillation experiments”, Chem. Eng. Sci., 53(5), 1067 (1998).
114.Prausnitz, J.M.; Lichtenthaler, R.N.; Azevedo, E.G. de. ”Molecular thermodynamics of fluid-phase equilibria” 3 rd edition; Prentice-Hall: New Jersey (1999).
115.Preston, K. L. ”Use of reactive distillation in the manufacture of MTBE”, US Patent 5,741,953 (1998).
116.Putman, H.M. ”Process for the removal of mercaptans”, US Patent 6,231,752 (2001).
117.Putman, H.M. ”Process for the desulfurization of a diesel fraction”, US Patent 6,338,793 (2002).
118.Qi, Z.; Sundmacher, K.; Stein, E.; Kienle, A.; Kolah, A. ”Reactive separation of isobutene fro C4 crack fractions by catalytic distillation process”, Separation and Purification Technology, 26(2-3), 147-163 (2002).
119.Rajamani, K.; Shenoy, C. S.; Rao, M. S.; Rao, M. G. “Kinetics of the hydrolysis of ethyl acetate catalysed by cation-exchange resin”, J. of Appl. Chem. Biotechnol., 28, 699 (1978).
120.Reid, R. C.; Prausnitz, J. M.; Poling, B. E. ”The properties of gases & liquids” 4th edition; McGraw-Hill: New York (1988).
121.Renon, H.; Prausnitz, J.M. ”Local compositions in thermodynamic excess functions for liquid mixtures”, AIChE J., 14, 135-144 (1968).
122.Rescalli, C. ”Process for synthetizing urea from ammonia and carbon dioxide, with total carbon dioxide conversion”, Europe patent 614,883 (1994).
123.Rhim, J.K.; Bae, S.Y.; Lee, H.T. ”Isothermal vapor-liquid equilibrium accompanied by esterification. ethanol-formic acid system”, Int. Chem. Eng., 25(3), 551-557 (1985).
124.Rivetti, F.; Paludetto, R.; Romano, U. ”Continuous process for the preparation of phenyl methyl carbonate”, US Patent 5,705,673 (1996).
125.Rodriguez, O.; Setinek, K. ”Dependence of esterification rates on crosslinking of ion exchange resins used as solid catalysts”, J. of Catal., 39, 449-455 (1975).
126.Saha, B.; Sharma, M.M. ”Esterification of formic acid, acrylic acid and methacrylic acid with cyclohexene in batch and distillation column reactors: ion-exchange resins as catalysts”, Reactive and Functional Polymers, 28(3), 263-278 (1996).
127.Saha, B. ”Recovery of dilute acetic acid through esterification in a reactive distillation column”, Catalysis Today, 60(1), 147-157 (2000).
128.Saito, S., Michishita T., Maeda, S., J. Chem. Eng. Japan, 4, 37 (1971).
129.Sanchez L.E.; Silverberg S. E.; Lattner J.R. ”Use of catalytic distillation to produce cyclopentane or cyclopentene”, US Patent 6,100,435, (2000).
130.Santacesaria E., Gelosa D., Danise P. “Vapor-phase esterification catalyzed by decationized y zeolites”, J. of catalysis, 80, 427-436 (1983).
131.Santiesteban J.G.; Levin D. ”Production of phenol using reactive distillation”, WO 0,146,102 (2001).
132.Savkovic-Stevanovic, J.; Misic-Vukovic, M.; Boncic-Caricic, G.; Trisovic, B.; Jezdic, S. “Reaction distillation with ion exchangers”, Separation Science and Technology, 27(5), 613-630 (1992).
133.Sawistowiski, H.; Pllavakls, A. ”Vapor-liquid equilibrium with association in both phases. Multicomponent system containing acetic acid”, J. Chem. Eng. Data, 27, 64-71 (1982).
134.Scates, M.O.; Parker, S.E.; Lacy, J.B.; Gibbs, R.K. ”Recovery of acetic acid from dilute aqueous streams formed during a carbonylation process”, US Patent 5,599,976 (1997).
135.Schleenstein, D.; Rasp, C.; Ronge, G.; Wilmes, O. ”Use of high boiling solvents or solvent mixtures as heat exchange medium in the thermal decomposition of carbamic esters”, European Patent 795,543 (1997).
136.Sebastiani, E.; Lacquaniti, L. ”Acetic acid-water system thermodynamical correlation of vapor-liquid equilibrium data”, Chem. Eng. Sci., 22, 1155-1162 (1967).
137.Segura, H.; Wisniak, J.; Aucejo, A.; Monton, J.B.; Munoz, R. ”Polyazeotropy in binary systems. 2. Association effects”, Ind. Eng. Chem. Res., 35, 4194-4202 (1996).
138.Shang, C. ”Dead oil catalytic distillation technology”, CN1056704 (1991).
139.Sharma, O.N.; Nageshwar, G. D.; Mene, P. S. ”Esterification of ethanol with propionic acid catalyzed by a cation exchange resin”, Indian J. of Technol., 11, 360 (1973).
140.Sharma, O.N.; Nageshwar, G.D.; Mene, P.S. ”Esterification of butanol with propionic acid catalyzed by cation exchange resin”, Chem. Ind. Dev., Incorporating CP&E, 11, 24 (1977).
141.Shoemaker, J.D.; Jones, E.M. “Cumene by catalytic distillation”, Hydroc. Process., 57 (1987).
142.Skrzypek, J.; Sadlowski, Jan Z.; Lachowska, M; Turzanski, M. ”Kinetics of the esterification of phthalic anhydride with 2-ethylhexanol. I. Sulfuric acid as a catalyst”, Chemical Engineering and Processing, 33(6), 413-418 (1994).
143.Skrzypek, J.; Sadlowski, Jan Z.; Lachowska, M.; Turzanski, M. ”Kinetics of the esterification of phthalic anhydride with 2-ethylhexanol. Part II. p-toluenesulphonic acid as a catalyst”, Chemical Engineering and Processing, 33(6), 455-457 (1995).
144.Smejkal, Q.; Hanika J.; Kolena J. ”2-Methylpropylacetate synthesis in a system of equilibrium reactor and reactive distillation column”, Chem. Eng. Sci., 56(2), 365-370 (2001).
145.Smejkal, Q.; oó , M. ”Comparison of computer simulation of reactive distillation using ASPEN PLUS and HYSYS software”, Chemical Engineering and Processing, 41(5) , 413-418 (2002).
146.Smith, L.A.; Huddleston, M.N., ”New MTBE design now commercial”, Hydroc. Process., 61(3), 121 (1982).
147.Smith, Jr., L.A. ”Catalytic distillation structure”, US Patent 4,443,559 (1984).
148.Smith, Jr., L.A. ”Catalytic distillation system”, US Patent 5,262,012 (1992).
149.Smith, J.M.; Van Ness, H.C.; Abbott, M.M. ”Introduction to chemical engineering thermodynamics”, 5th edition, McGraw-Hill (1996).
150.Smith, Jr., L.A. ; Arganbright, R.P. ”Process for making acetals”, US Patent 6,015,875 (2000).
151.Sneesby, M.G.; Tade, M.O.; Datta, R.; Smith, T.N. ”ETBE synthesis via reactive distillation. 1. Steady-state simulation and design aspects”, Ind. Eng. Chem. Res., 36(5), 1855-1869 (1997).
152.Song, W.; Venimadhavan, G.; Manning, J.M.; Malone, M.F.; Doherty, M.F. “Measurement of residue curve maps and heterogeneous kinetics in methyl acetate synthesis”, Ind. Eng. Chem. Res., 37, 191 (1998).
153.Sristava, R.; Smith, B.D. ”Total pressure vapor liquid equilibrium data for binary systems of diethylamine with acetone, acetonitrile and methanol”, J. Chem. Eng. Data, 30, 308-313 (1985).
154.Steynberg P.J.; Denga Z.; Steyn R.; Bezuidenhout B.C.; Stark N.L. ”Production of amides and/or acids from nitriles”, US Patent 6,100,427 (2000).
155.Subawalla, H.; Gonzalez, J.C.; Seibert, A.F.; Fair, J.R. ”Capacity and efficiency of reactive distillation bale packing: Modeling and experimental validation”, Ind. Eng. Chem. Res., 36, 3821-3832 (1997).
156.Sullivan, D. A. ”Solvent selection in today’s regulatory environment”, Modern Paint and Coatings, November, 38 (1995).
157.Sundmacher, K.; Hoffmann, U. ”Activity evaluation of a catalytic distillation packing for MTBE production”, Chemical Engineering & Technology, 16(4), 279-289 (1993).
158.Sundmacher, K.; Hoffmann, U. ”Multicomponent mass and energy transport on different length scales in a packed reactive distillation column for heterogeneous catalyzed fuel ether production”, Chem. Eng. Sci., 49, 4443-4464 (1994).
159.Sundmacher, K. “Development of a new catalytic distillation process for fuel ethers via a detailed nonequilibrium model”, Chem. Eng. Sci., 51, 2359—2368 (1996).
160.Tamir, A.; Wisniak, J. “Vapor equilibrium in associating systems (water-formic acid-propionic acid)”, Ind. Eng. Chem. Fundam., 15, 274-280 (1976).
161.Tamura, K.; Nagata, I. ”Thermodynamics of liquid mixtures of acids. i. liquid-phase association constants for alkanoic acids from the properties of pure fluids”, Fluid Phase Equilib., 64, 49-60 (1991).
162.Tanner K. I. ”Method for recovering acetone”, WO Patent 9,712,654 (1997).
163.Tau, L.M.; Burtron H.D. ”Acid catalyzed of ethyl tertiary butyl ether (ETBE)“, Applied Catalysis, 53, 263-271 (1989).
164.Taylor, R.; Krishna, R. ”Modelling reactive distillation”, Chem. Eng. Sci., 55, 5183-5229 (2000).
165.Tejero, J.; Creus, E.; Iborra, M.; Cunill, F.; Izquierdo, J.F.; Fité, C. ”Comparative study of IPTBE synthesis on HZSM-5 and ion-exchange resin catalysts”, Catalysis Today, 65(2-4), 381-389 (2001).
166.Travers C.; Capron P.; Lebas E.; Jullian S.; Thery M.; Joly J.F. ”Paraffin isomerisation process using reactive distillation”, US Patent 5,948,948, 1999.
167.Trimble, H.M.; Richandson, E.L. “Equilibrium in an esterification reaction with perchloric acid as catalyst”, J. Am. Chem. Soc., 62, 1018-1019 (1940).
168.Triplett, T. ”Market shift to safer solvents”, Industrial Paint & Powder, 72(12), 44-47 (1996).
169.Trubac, R.E.; Dautzenberg, F.M.; Griffin, T.A.; Paikert, B.; Schmidt, V.R.; Overbeek, R.A. ”Micro-engineered catalyst systems: ABB’s advancement in structured catalytic packings”, Catalysis Today, 69(1-4), 17-24 (2001).
170.Van Baten, J.M.; Krishna, R. ”Liquid-phase mass transfer within KATAPAK-S® structures studied using computational fluid dynamics simulations”, Catalysis Today, 69(1-4), 371-377 (2001).
171.Vassena, D.; Kogelbauer, A.; Prins, R. “Potential routes for the nitration of toluene and nitrotoluene with solid acids”, Catalysis Today, 60(3), 275-287 (2000).
172.Venkataraman, S.; Chan, W.K.; Boston, J.F. “Reactive distillation using ASPEN PLUS”, Chem. Eng. Prog., 86(8), 45-54 (1990).
173.Venkateswarlu, K.; Sinha, R.; Rao, R. J. “Kinetics of esterification of n-butanol with propionic acid in a stirred tank batch reactor”, Chemicals and Petrochemicals J. (1976).
174.Von Scala, C.; Götze, L.; Moritz, P. “Acetate technology using reactive distillation”, Sulzer technical review, Sulzer chemtech AG. Switerland, 3, 12-15 (2001).
175.Vora, B.V. “Process for the production of butene-1 from a mixture of C4 olefins”, US Patent 6,156,947 (2000).
176.Voss, B. “Acetic acid reactive distillation process based on DME/methanol carbonylation”, US Patent 6,175,039 (2001).
177.Walas, S.M. “Phase equilibria in chemical engineering”, Butterworth: Boston, USA (1985).
178.Wang, Q.L.; Ma, Y.; Yan, H.; Ji, X.; Qiu, Q. “Zeolite-catalyzed esterification I. Synthesis of acetates, benzoates and phthalates”, Applied Catalysis A: General, 139(1-2), 51-57 (1996).
179.Ward D.J. “Etherification of isoamylenes”, US Patent 5,196,612 (1993).
180.Wassel, M.A “Thermodynamic of catalytic esterifucation of ethanol with carboxylic acids by mixed oxide (nio-moo3) a catalyst”, Rass. Chim. 43(3), 103-107 (1991).
181.Watson, D.J.; Williams, B.L.; Muskett, M.J.; Smith, S.J.; Nguyen, C.T.; Baker, L.I., “Process for the production of acetic acid”, US Patent 5,831,120 (1998).
182.Wilson, G. M. “Vapor-liquid equilibrium. XI: A new expression for the excess free energy of mixing”, J. Am. Chem. Soc., 86, 127-130 (1964).
183.Xu, X.; Zhao, Z.; Tian, S.J. “Study on catalytic distillation processes, Part III. Prediction of pressure drop and holdup in catalyst bed”, Chemical Engineering Research and Design, Transactions of the Institution of Chemical Engineers, Part A, 75, 625-629 (1997).
184.Xu, X.; Zhao, Z.; Tian, S.J. “Study on catalytic distillation processes, Part IV: Axial dispersion of liquid in catalyst bed of catalytic distillation column”, Chemical Engineering Research and Design, Transactions of the Institution of Chemical Engineers, Part A, 77, 16-20 (1999).
185.Xu, Z.P.; Chuang, K.T. “Kinetics of acetic acid esterification over ion exchange catalysts”, Can. J. Chem. Eng., 74, 493 (1996).
186.Xu, Z. P.; Chuang, K. T. “Effect of internal diffusion on heterogenous catalytic esterification of acetic acid”, Chem. Eng. Sci., 52, 3011 (1997).
187.Xu, Z.P.; Chuang, K.T. “Apparatus for catalytic distillation”, US Patent 6,045,762 (2000).
188.Yadav, G.D.; Mehta, P.H. “Heterogeneous catalysis in esterification reactions: preparation of phenethyl acetate and cyclohexyl acetate by using a variety of solid acidic catalysts”, Ind. Eng. Chem. Res., 33(9), 2198-2208 (1994).
189.Yadav, G.D.; Kulkarni, H.B. ”Ion-exchange resin catalysis in the synthesis of isopropyl lactate”, Reactive and Functional Polymers, 44(2), 153-165 (2000).
190.Yang, Z. ”Esterification-distillation of butanol and acetic acid”, Huagong Xuebao(China), 49(1), 39-47 (1998).
191.Yue, P. L.; Olaofe, O. ”Kinetic analysis of the catalytic dehydration of alcohols over zeolites”, Chemical Engineering Research & Design, 62(2), 81-91 (1984).
192.Zheng, Y.; Xu, X. “Study on catalytic distillation processes. Part II. Simulation of catalytic distillation processes, quasi homogeneous rate based model”, Chem. Eng. Res. Des., Trans. Instn. Chem. Engrs, Part A, 70, 465—470 (1992).
193.Zoeller, J.R.; Lane, D.W.; Cwirko, E.H. ; Fuller, Jr., D.W.; Barnicki, S.D. ”Process for generating vinyl carboxylate esters”, US Patent 5,821,384 (1998).
194.唐川公一，”汽液接觸裝置”，日本特許公報，昭46-31321 (1971).
195.王志亮、葉明湯、楊宗仁、梅曼、陶偉強、王偉，”催化反應精餾塔及其用途”，CN1060228 (1992).
196.張全勝, ”催化蒸餾反應器觸媒填充物發展概況”, 觸媒與製程, 4(1), 83-89 (1995).
197.蓋旭東，“反應蒸餾分離技術進展”，現代化工，第五期，17 (1995).
198.李永紅、劉家祺、馬沛生，”萃取反應精餾合成高純度乙酸乙酯”，石油化工，10,719 (1996).
199.屈一新, 汪文川, 秦其光, 陳濱, “丙酸和甲醇酯化反應動力學及其化學反應平衡的研究”, 化工學報, 48(5), 576-583 (1997).
200.肖劍、劉家祺，”催化精餾塔催化劑裝填技術研究進展”，化工進展, 2, 8-11, (1999).
201.韓明漢、林鴻飛、汪展文、金涌， ”催化蒸餾反應器的新型內構件的研究 I.內構件的性能”, 石油化工, 29, 674-677 (2000).
202.楊梅、韓運華、張啟忠、金朝輝、丁斌, ”催化蒸餾合成丙烯酸丁酯”, 吉林化工學院學報, 17(1), 22-24 (2001).
203.郭建麟，”異相反應蒸餾系統”， 碩士論文，國立台灣科技大學 (2001).
204.劉勁松、朱思強、白鵬、楊志才，”催化精餾塔催化劑裝填技術研究進展”，化工機械，28(5), 299-302 (2001).