本論文提出一創新之裝置，係針對已提出之併合熱與物質交換薄膜模組(Hybrid heat and mass exchange membrane module)之修正設計。此設計使用殼管式多膜管裝置，液相以落膜方式於膜管外與氣相進行熱質傳，熱交換流體於膜管內與管外之氣相或液相進行熱傳。應用此設計之蒸餾塔，即HMEDiC (Heat and Mass Exchange Distillation Column)，屬於非絕熱(Diabatic)操作，可獲接近熱力學可逆之操作，提高能效。本論文針對氨水系統與苯－甲苯系統完成了HMEDiC之模擬分析研究。模擬分析使用Aspen Plus程序模擬軟體，配合以Fortran程式語言撰寫之嚴謹熱力學數學模式，並利用FLUENT軟體進行流力分析，決定最小膜厚。
    針對氨水系統之分析結果顯示，在最小膜厚下，HMEDiC之熱能消耗低於填充式蒸餾塔。對氨水系統與苯－甲苯系統，具塔內熱交換之HMEDiC可操作於不具塔內熱交換時之兩倍進料流量，而單位進料之精餾段熱負荷、單位進料之氣提段熱負荷、單位進料之全塔可用能損失皆較低。HMEDiC之ㄧ重要特性為當進料流量固定時，並非膜厚愈小，產物純度愈高。當操作於具塔內熱交換之情況時，改變熱質傳係數之影響不大。

An innovative device is proposed which is a revised design of a previously reported hybrid heat and mass exchange membrane module. The revised design make use of shell and tube type module. In the module, liquid forms a falling film at the tube outside and contacts with the shell side vapor phase, besides, heating or cooling fluid flows inside the membrane tube for heat exchange with the tube outside liquid or vapor phases. The module acts as a distillation, named HMEDiC (Heat and Mass Exchange Distillation Column) is investigated. The diabatic operation allows approching to thermodynamic reversible condition and increasing of energy efficiency. Applications of HMEDiC on ammonia-water and benzene-toluene systems are studied. For the HMEDiC, a rigorous mathematical model established on Aspen Plus with attached Fortran program is developed. Minimum flowrate required for forming a complete liquid film around the tube outside is determined by using the CFD package, FLUENT.

    For ammonia-water system, under the minimum film thickness operation, energy consumption of a HMEDiC is lower than that of a packed column. For both ammonia-water and benzene-toluene systems, HMEDiC with and without column inside heat exchange are compared and the former allows about two times higher feed flowrate and significantly lower energy consumption in terms of per unit feed flowrate heat loads of rectification section and stripping section as well as exergy loss per unit feed flowrate. An important characteristic found is that for a fixed feed flowrate, decreasing of film thickness does not necessarily results in increasing of product purity. For a HMEDiC with column inside heat exchange, the effects of heat and mass transfer coefficients are not significant.

誌謝......................................................i
中文摘要................................................ii
英文摘要...............................................iii
目錄.....................................................iv
圖目錄..................................................vii
表目錄..................................................xiv
第一章 前言...............................................1
第二章 文獻回顧...........................................3
第三章 熱與物質併合交換器蒸餾塔(HMEDiC)..................11
3.1 蒸餾系統配置.........................................11
3.2 併合熱質傳單元數學模式...............................16
3.2.1 精餾段併合熱質傳單元數學模式.......................16
3.2.2 氣提段併合熱質傳單元數學模式.......................23
3.3 填充式蒸餾塔數學模式.................................29
第四章 落膜系統最小膜厚之計算流體力學分析................32
4.1 數學模式.............................................32
4.2 計算流體力學模擬.....................................37
4.2.1 使用FLUENT之模式設定..............................41
4.3 分析結果............................................43
4.3.1 水系統.............................................43
4.3.2 苯系統.............................................52
第五章 HMEDiC塔內特性分析.............................61
5.1 氨水系統...........................................61
5.1.1 基本個案條件設定................................61
5.1.2 熱能分析.........................................64
5.1.3 塔內特性分析......................................66
5.2 苯-甲苯系統..........................................77
5.2.1 基本個案條件設定.............................77
5.2.2 熱能分析...........................................80
5.2.3 塔內特性分析......................................82
第六章 HMEDiC性能模擬分析................................93
6.1 氨水系統.............................................93
6.1.1 HMEDiC與填充塔之比較.............................93
6.1.2 改變進料流量與膜厚的影響..........................111
6.1.3 改變熱質傳係數之影響.............................119
6.2 苯-甲苯系統.........................................121
6.2.1 改變進料流量與膜厚的影響..........................121
6.2.2 改變熱質傳係數之影響..............................131
第七章 結論............................................133
符號說明...............................................136
參考文獻................................................140
附錄A 膜厚分析結果相關圖-不同管徑......................144
附錄B HMEDiC個案模擬結果................................147

圖目錄
圖2.1 HiDiC 與 DiDiC......................................4
圖2.2 薄膜吸收器與蒸餾塔................................6
圖2.3 中空纖維式併合熱與物質交換薄膜模組...............8
圖2.4 修正之併合熱與物質交換薄膜模組.................10
圖3.1 HMEDiC系統.........................................11
圖3.2 精餾段膜管配置...................................13
圖3.3 氣提段膜管配置...................................13
圖3.4 Aspen Plus系統流程................................15
圖3.5 併合熱與物質交換單元(HME).........................15
圖3.6 精餾段第n段HME之進出物流與熱質傳通量示意圖.........18
圖3.7 氣提段第n段HME之進出物流與熱質傳通量示意圖.........25
圖3.8 填充塔系統第n段之進出物流與熱質傳通量示意圖........30
圖4.1 管外(a)完整液膜與..................................33
圖4.1 管外(b)細流之示意圖................................33
圖4.2 GAMBIT軟體網格繪製功能.............................39
圖4.3 細流之GAMBIT網格架構圖.............................40
圖4.4 水系統速度分佈(a)進口面............................44
圖4.4 水系統速度分佈(b)出口面............................44
圖4.4 水系統速度分佈(c)中間對稱面........................45
圖4.5 水系統壓力分佈-對稱面............................45
圖4.6 水系統速度分佈(a)進口面............................46
圖4.6 水系統速度分佈(b)出口面...........................46
圖4.6 水系統速度分佈(c)中間對稱面..................47
圖4.7 水系統壓力分佈-對稱面..............................47
圖4.8 管外液膜流量對α角.................................50
圖4.9 管外液膜動能對α角..................................50
圖4.10 完整液膜與細流之流量與相對能關係-F1個案...........51
圖4.11 完整液膜與細流之流量與相對能關係圖-F2個案.........51
圖4.12 苯系統速度分佈圖(a)進口面.........................51
圖4.12 苯系統速度分佈圖(b)出口面..............53
圖4.12 苯系統速度分佈圖(c)中間對稱面..............54
圖4.13 苯系統壓力分佈圖-對稱面..............54
圖4.14 苯系統速度分佈圖(a)進口面..............55
圖4.14 苯系統速度分佈圖(b)出口面..............55
圖4.14 苯系統速度分佈圖(c)中間對稱面..............56
圖4.15 苯系統壓力分佈圖－對稱面..............56
圖4.16 苯系統管外液膜流量對α角圖..............59
圖4.17 苯系統管外液膜動能對α角圖..............59
圖4.18 完整液膜與細流之流量與相對能關係圖-F3個案.........60
圖4.19 完整液膜與細流之流量與相對能關係圖-F4個案.........60
圖5.1 氨水系統塔內溫度分佈-基本個案(a)A-1(b)A-2..........67
圖5.2 氨水系統塔內氨成份濃度分佈-基本個案(a)A-1(b)A-2....68
圖5.3 氨水系統塔內總莫耳通量分佈-基本個案(a)A-1(b)A-2....70
圖5.4 氨水系統塔內氨成份莫耳通量分佈-基本個案(a)A-1(b)A-2...71
圖5.5 氨水系統塔內水成份莫耳通量分佈-基本個案(a)A-1(b)A-2.....72
圖5.6 氨水系統塔內熱交換量分佈-基本個案(a)A-1......73
圖5.6 氨水系統塔內熱交換量分佈-基本個案(b)A-2........74
圖5.7 氨水系統氣液組成-基本個案..............74
圖5.8 氨水系統塔內可用能損失分佈-基本個案(a)A-1(b)A-2......76
圖5.9 苯-甲苯系統溫度之塔內分佈圖-基本個案(a)B-1(b)B-2.......83
圖5.10 苯-甲苯系統塔內苯成份濃度分佈圖-基本個案(a)B-1(b)B-2.......84
圖5.11 苯-甲苯系統塔內總莫耳通量分佈圖-基本個案(a)B-1(b)B-2......86
圖5.12 苯-甲苯系統成份苯莫耳通量之塔內分佈圖-基本個案(a)B-1(b)B-2.................87
圖5.13 苯-甲苯系統塔內甲苯莫耳通量分佈圖-基本個案(a)B-1(b)B-2.....................88
圖5.14 苯-甲苯系統塔內熱交換分佈圖-基本個案(a)B-1..............89
圖5.14 苯-甲苯系統塔內熱交換分佈圖-基本個案(b)B-2..............90
圖5.15 苯-甲苯系統塔內氣液組成分佈圖-基本個案..............90
圖5.16 苯-甲苯系統可用能損失分佈圖-基本個案(a)B-1..............91
圖5.16 苯-甲苯系統可用能損失分佈圖-基本個案(b)B-2..............92
圖6.1 塔內溫度分佈(a)C-1..............99
圖6.1 塔內溫度分佈(b)C-6..............99
圖6.1 塔內溫度分佈(c)C-7..............100
圖6.2 氨水系統塔內氨成份濃度分佈(a)C-1..............100
圖6.2 氨水系統塔內氨成份濃度分佈(b)C-6..............101
圖6.2 氨水系統塔內氨成份濃度分佈(c)C-7..............101
圖6.3 塔內總莫耳通量分佈(a)C-1..............102
圖6.3 塔內總莫耳通量分佈(b-1)C-6..............102
圖6.3 塔內總莫耳通量分佈(b-2)C-6..............103
圖6.3 塔內總莫耳通量分佈(c)C-7..............103
圖6.4 塔內氨成份莫耳通量分佈(a)C-1..............104
圖6.4 塔內氨成份莫耳通量分佈(b-1)C-6..............104
圖6.4 塔內氨成份莫耳通量分佈(b-2)C-6................105
圖6.4 塔內氨成份莫耳通量分佈(c)C-7..............105
圖6.5 塔內水成份莫耳通量分佈(a)C-1..............106
圖6.5 塔內水成份莫耳通量分佈(b)C-6..............106
圖6.5 塔內水成份莫耳通量分佈(c)C-7..............107
圖6.6 塔內熱交換分佈(a)C-1..............107
圖6.6 塔內熱交換分佈(b)C-6...........................108
圖6.6 塔內熱交換分佈(c)C-7..............108
圖6.7 塔內可用能分佈(a)C-1..............109
圖6.7 塔內可用能分佈(b)C-6..............109
圖6.7 塔內可用能分佈(c)C-7..............110
圖6.8 氨水系統產物純度與膜厚之關係..............116
圖6.9 氨水系統進料流量與膜厚對精餾段能耗之影響-無熱交換..............117
圖6.10 氨水系統進料流量與膜厚對氣提段能耗之影響-無熱交換..............117
圖6.11 氨水系統進料流量與膜厚對精餾段能耗之影響-有熱交換..............118
圖6.12 氨水系統進料流量與膜厚對氣提段能耗之影響-有熱交換..............118
圖6.13 氨水系統熱質傳係數對精餾段能耗之影響..............120
(MF=transfer coeff./transfer coeff. of base case)
圖6.14 氨水系統熱質傳係數對氣提段能耗之影響..............120
(MF=transfer coeff./transfer coeff. of base case)
圖6.15 苯-甲苯系統產物純度與膜厚之關係..............128
圖6.16 苯-甲苯系統進料流量與膜厚對精餾段能耗之影響-無熱交換..............129
圖6.17 苯-甲苯系統進料流量與膜厚對氣提段能耗之影響-無熱交換...............129
圖6.18 苯-甲苯系統進料流量與膜厚對精餾段能耗之影響-有熱交換...............130
圖6.19 苯-甲苯系統進料流量與膜厚對氣提段能耗之影響-有熱交換...............130
圖6.20 苯-甲苯系統熱質傳係數對精餾段能耗之影響..............132
(MF=transfer coeff./transfer coeff. of base case)
圖6.21 苯-甲苯系統熱質傳係數對氣提段能耗之影響..............132
(MF=transfer coeff./transfer coeff. of base case)
圖A.1 液體在管外流動α角改變對流速之效應-不同管徑(n=1)..............144
圖A.2 液體在管外流動α角改變對動能之效應-不同管徑(n=1)..............144
圖A.3 膜流動與細流之流速與相對能關係圖- D=0.03cm..............145
圖A.4 膜流動與細流之流速與相對能關係圖- D=0.1cm..............145
圖A.5 膜流動與細流之流速與相對能關係圖- D=0.3cm..............146
圖A.6 膜流動與細流之流速與相對能關係圖- D=0.6cm..............146
 
表目錄
表4.1 邊界層及網格設定..............38
表4.2 FLUENT模擬個案..............42
表4.3 FLUENT模擬個案邊界條件設定..............42
表4.4 細流數n=1之結果- F1個案..............48
表4.5 膜流動之計算結果- F1個案 ..............48
表4.6 細流數n=1之結果-F2個案..............48
表4.7 膜流動之計算結果-F2個案..............49
表4.8 細流數n=1之結果-F3個案..............57
表4.9 膜流動之計算結果- F3個案..............57
表4.10 細流數n=1之結果- F4個案......................57
表4.11 膜流動之計算結果- F4個案...................58
表5.1 氨水系統HMEDiC裝置尺寸－基本個案 ..................62
表5.2 氨水系統HMEDiC操作條件設定值－基本個案.............63
表5.3 氨水系統個案熱能分析..............65
表5.4 苯-甲苯系統HMEDiC裝置尺寸..............78
表5.5 苯-甲苯系統基本個案設計條件..............79
表5.6 苯-甲苯系統個案熱能分析........................81
表6.1 氨水系統填充塔裝置尺寸..............93
表6.2 氨水系統HMEDiC之裝置尺寸－與填充塔比較個案..............94
表6.3 填充塔模擬結果之比較..............94
表6.4 氨水系統HMEDiC操作條件設定值－與填充塔比較個案...96
表6.5 氨水系統填充塔與HEMDiC之能耗比較..............97
表6.6 氨水系統HMEDiC之裝置尺寸-進料流量與膜厚影響分析個案 ..............112
表6.7 氨水系統HMEDiC操作條件設定值－進料流量與膜厚影響分析個案..............113
表6.8 氨水系統HMEDiC模擬結果－進料流量與膜厚影響分析..............115
表6.9 苯-甲苯系統HMEDiC之裝置尺寸-進料流量與膜厚影響分析個案..............122
表6.10 苯-甲苯系統HMEDiC操作條件設定值－進料流量與膜厚影響分析個案..............123
表6.11 苯-甲苯系統HMEDiC模擬結果－進料流量與膜厚影響分析..............124
表6.12 苯-甲苯系統HMEDiC模擬結果－進料流量與膜厚影響分析 (續)..............126
表B.1 系統分析物流資料表 A-1個案..............147
表B.2 系統分析物流資料表 A-2個案..............148
表B.3 系統分析物流資料表 A-3個案..............149
表B.4 系統分析物流資料表 A-4個案..............150
表B.5 系統分析物流資料表 B-1個案..............151
表B.6 系統分析物流資料表 B-2個案..............152
表B.7 系統分析物流資料表 B-3個案..............153
表B.8 系統分析物流資料表 B-4個案..............154
表B.9 系統分析物流資料表 C-1個案..............155
表B.10 系統分析物流資料表 C-6個案..............156
表B.11 系統分析物流資料表 C-7個案..............157

Bird, R. B., W. E. Stewart and E. N. Lightfoot, Transport Phenomena, John Wiley & Sons, Inc., New York, 1960.

Colburn A. P. and T. B. Drew, “The condensation of mixer vapors. Transactions” AIChE J., vol. 33, pp. 197-215, 1937.

Chen, J., H. Chang and S. R. Chen, “Simulation study of a hybrid  absorber-heat exchanger using hollow fiber membrane module for the ammonia-water absorption cycle,” Int. J. Refrig., Vol. 29, pp. 1043-1052, 2006.

Fernández-Seara, J., J. Sieres and M. Vázquez, “Simultaneous heat and mass transfer of a packed distillation column for ammonia-water absorption refrigeration systems,” Int. J. Therm. Sci., vol. 41, pp. 927-935, 2002.

Geankoplis, C. J., Mass Transpot Phenomena, Holt, Rinehart and Winston, Inc., New York, N.Y., pp. 266-267, 1972.

Hughes, D. T. and T. R. Bott, “Minimum thickness of a liquid film flowing down a vertical tube,” Int. J. Heat Mass Trans. vol. 41, n. 2, pp. 253-260, 1998.

Hausen, H., “Därstellung des Warmeuberganges in Rohren durch verallgemeinerte Potenzbeziehungen,” VDI Z., n. 4, pp. 91, 1943.

Holman, J. P., Heat Transfer, McGraw-Hill, Inc., pp. 493-494, 1989.

Israelachvili, J., Intermolecular and surface forces, 2nd ed., Chapter 15, Academic Press, New York, 1991.

Jaycock, M. J. and G. D. Parfitt, Chemistry of interfaces, Chapter 5, Ellis Horwood, 1981.

Jimenez, E. S., P. Salamon, R. Rivers, C. Rendon, K.H. Hoffmann, M. Schaller, and B. Andresen, “Optimization of a diabatic distillation column with sequential heat exchangers,” Ind. Eng. Chem. Res., vol. 43, pp. 7566-7571, 2004.

Kaeser, M. and C. L. Pritchard, “Heat transfer at the surface of sieve trays,” Chem. Eng. Res. Des., vol. 83(A8), pp. 1038-1043, 2005.

King, C. J., Separation Process, 2nd Ed., McGraw-Hill, Inc., New York, 1981.

Liang, S. Y. and W. Smith, “The effect of heat transfer between the phases on the performance of countercurrent distillation columns,” Chem. Eng. Sci., vol. 17, pp. 11-21, 1962.

Nakaiwa, M., M. Owa, T. Akiya, V. Lueprasitsakul, and T. Takamatsu, “Operating pressure of a plate-to-plate heat-integrated distillation column,” Kagaku Kogaku Ronbunshu, vol. 14, pp. 63, 1988.

Nakaiwa, M., K. Hwang, T. Endo, T. Akiya, and T. Takamatsu, “Internally heat-integrated distillation columns: a review,” Trans. IChemE, Part A, Chem. Eng. Res. Des., vol. 81, pp. 162-177, 2003.

Onda, K., H. Takeuchi and Y. Okumoto, “Mass transfer coefficients between gas and liquid phases in packed columns,” J. Chem. Eng., Jpn., 1, pp. 56-62, 1968.

Prasad, R. and K. K. Sirkar, “Hollow fiber solvent extraction of pharmaceutical products : A case study,” J. Mem. Sci., vol. 47, n. 3, pp. 235-259, 1989

Rivero R., L’Analyse d’Exergie: Application à la Distillation Diabatique et aux Pompes à Chaleur à Absorption. Nancy: Institut National Polytechnique de Lorraine, 1993.

Sirkar, K. K., Other new membrane processes, in: Ho, W. S. W. and K. K. Sirkar (Eds.), Membrane Handbook, Chapman & Hall, New York, 1992.

Sieres, J. and J. Fernández-Seara, “Mass transfer characteristics of a structured packing for ammonia rectification in ammonia-water absorption refrigeration systems,” Int. J. Refrig., vol. 30, pp. 58-67, 2007.

Smith, W., “The effects of thermal distillation on the performance of differential-contact distillation column,” Chem. Eng. Sci., vol. 39, n. 6, pp. 997-1003, 1984.

Zhang, G. and E. L. Cussler, “Distillation in Hollow Fibers,” AIChE J., vol. 49, n. 9, pp. 2344-2351, 2003.

Zhang, G. and E. L. Cussler, “Hollow fiber as structured distillation packing,” J. Mem. Sci., vol. 215, pp. 185-193, 2003.

Zaheed, L. and R. J. J. Jachuck, “Review of polymer compact heat exchangers, with special emphasis on a polymer film unit,” Appl. Therm. Eng., vol. 24, pp. 2323-2358, 2004.

Zaheed, J., Cross-corrugated polymer film compact heat exchanger (PFCHE), Ph. D. Thesis, School of Chemical and Advanced Materials, University of Newcastle Upon Tyne, UK, 2003.

Zarkadas, D. M. and K. K. Sirkar, “Polymeric Hollow Fiber Heat Exchangers: An Alternative for Lower Temperature Applications,” Ind. Eng. Chem. Res., vol. 43, pp. 8093-8106, 2004.