生質柴油具有低污染及永續再生之優點，一般原料來源為動植物油脂，例如:大豆、廢油和油菜籽可再生利用作為原料，利用動植物油脂加上低分子的醇類經由催化劑轉酯化過程即可得到生質柴油。
本研究使用CHEMCAD®化工製程軟體，台灣生質柴油標準CNS-15072為規範，以三油酸甘油酯（C57H104O6）代表大豆油為原料，進行（1）典型雙反應器系統、（2）甘油相逆迴流雙反應器系統、（3）甘油相自迴流雙反應器系統、（4）甘油相自迴流單反應器系統，四個鹼性反應架構之生質柴油製程探討。分析結果以甘油相迴流單反應器系統成本最低，而雙反應器系統中則以甘油相自迴流雙反應器系統成本最低，較典型雙反應器系統低17%。
本研究以熱力學模式UNIQUAC迴歸生質柴油/甘油/甲醇液液平衡，與預測之UNIFAC模式比較，因UNIFAC模式計算之沉降槽甲醇溶解度較低，由UNIFAC預測模擬之沉降槽體積較大，而所需之醇油比亦較高。

Biodiesel is one of the mostly used renewable fuels in the world, which has the advantages of low pollutant emissions and sustainability. The feedstocks for biodiesel production can be animal fats or vegetable oils such as tallow, waste cooking oil, soybean oil and rapeseed oil. Biodiesel can be produced from these fats or oils with alcohol through transesterification reaction.
In this study, the commercial simulator CHEMCAD® is used to analyze the alkaline-catalyzed biodiesel processes. Four alkaline-catalyzed processes were analyzed: (1) traditional two-reactor process (2) glycerol phase recycle two-reactor process (3) glycerol phase self-recycle two-reactor process (4) glycerol phase recycle one-reactor process. The unit cost of biodiesel for glycerol phase recycle one-reactor process is the lowest. Among the two-reactor processes, the cost for the glycerol phase self-recycle two-reactor process is the lowest, which is 17% lower than the traditional two-reactor process.
The liquid-liquid equilibrium of biodiesel/glycerol/methanol is regressed from literature experimental data by UNIQUAC model in this study. Comparing the QNIQUAC and predictive UNIFAC models, the UNFAC model predicts larger decanter and higher alcohol to oil ratio.

摘 要 i
Abstract ii
誌 謝 iii
目 錄 iv
圖 目 錄 vi
表 目 錄 vii
第一章 緒論 1
1-1前言 1
1-2研究動機與目的 4
第二章 文獻回顧 5
2-1生質柴油料源 5
2-2生質柴油製程相關研究 8
2-2-1鹼性觸媒 8
2-2-2酸性觸媒 10
2-2-3超臨界流體反應 11
2-2-4酵素催化反應 12
2-2-5固體觸媒製程 13
2-3生質柴油規範 15
2-4反應動力學 18
2-5熱力學模式 23
2-6生質柴油製程分析 24
第三章 生質柴油製程模擬 27
3-1系統成分 27
3-2轉酯化反應動力學 28
3-3熱力學模式 29
3-4反應器系統分析 32
3-4-1單反應器系統(I) 32
3-4-2單反應器系統(II) 33
3-4-3雙反應器系統(I) 35
3-4-4雙反應器系統(II) 36
3-4-5雙反應器系統(III) 37
3-5反應器系統比較 39
3-6-1設計基準 40
3-6-2總年成本分析 41
3-6-3生質柴油製程設計原則 41
3-6-4單反應器系統(II) 42
3-6-5雙反應器系統(I) 44
3-6-6雙反應器系統(II) 46
3-6-7雙反應器系統(III) 48
第四章 結果與討論 50
4-1各製程之分析比較 50
4-2製程設計熱力學比較 54
第五章 結論 55
參考文獻 56
附錄A 計算TAC使用之公式 61
附錄B 反應系統質能平衡結果 64
附錄C 生質柴油檢驗方法 78

Andreatta, E. A.; Lidia, M. C.; Hegel, P.; Susana, B. B. and Esteban Brignole, A.B., “Phase Equilibria in Ternary Mixtures of Methyl Oleate, Glycerol, and Methanol”, Ind. Eng. Chem. Res. 47, 5157-1564, 2008.
AspenTech, “Using Aspen Plus to model production of biodiesel from vegetable oil”, Aspen Plus requested example No. 121, 249, 2007. (Available electronically at http://support.aspentech.com)
Batista, E.; Monnerat, S.; Stragevitch, L.; Pina, C. G.; Goncalves, C. B. and Meirelles, A. J. A., “Prediction of liquid-liquid equilibrium for systems of vegetable oils fatty acids and ethanol”, Journal of chemical and engineering data, 44, 1365-1369, 1999.
Basu, H. N. and Norris, M. E., ”Process for production of esters for use as adiesel fuel substitute using a non-alkaline cat-alyst”, US Patent, 55, 25-126, 1996.
Biswas, S. K. N. and Srikanth, G., “Biodiesel: Technology & Business Opportunities–An Insight”, Proceedings of the biodiesel conference toward energy independance - Focus of Jatropha. 303-330, Edited by B. Singh, Swaminathan R. and Ponraj V., Hyderabad, India, 2006.
Boocock, D. G. B.; Konar, S. K. and Sidi, H., “Phase diagrams for oil/methanol/ester
mixtures”, JAOCS, 73, 548-559, 1996.
BP, statistical review of world energy. UK, British petroleum., 2007.
Bradshaw, G. B. and Meuly, W. C., “Process of making pure soaps”, U.S. patent No.
2, 271, 619, E.I. duPont de Nemours & Company, Wilmington, Delaware, USA, Feb, 1942.
Cao, W.; Han, H. and Zhang, J., “Preparation of biodiesel from soybean oil using
supercritical methanol and co-solvent.”, Fuel, 84, 347-351, 2005.
Ceriani, R. and Meirelles, A. J. A., “Predicting vapor-liquid equilibria of fatty systems”,
fluid phase equilibria, 215, 227-236, 2004.
Chuang, C. W.; Goff, M. J. and Galen, J., “Distribution of Methanol and Catalysts between Biodiesel and Glycerin Phases.”, 1274-1278, 2005.
Connemann, J.; Krallmann, A. and Fischer, E., “Process for the continuous production
of lower alkyl esters of higher fatty acids”, U.S. Patent No.5, 354, 878, 1994.
Darnoko, D. and Munir, C.,“Kinetics of Palm Oil Transesterification in a Batch
Reactor”, 2000. (http://www.fineprint.com).
Ebiura, T. and Echizen, T., “Selective transterification of triolein with methanol to
methyl oleate and glycerol using alumina loaded with alkali metal salt as a solid –base catalyst”, Applied Catalysis A, General 283, 111-116 , 2005.
Ebiura, T.; Echizen, T.; Ishikawa, A.; Murai, K. and Selective, T., “transesterification of
triolein whit methanol to methyl oleate and glycerol using alumina loaded with alkali metal salt as a solid-base catalyst”, Applied Catalysis A, Genera 283, 111-116, 2005.
Freedman, B.; Pryde, E. H. and Mounts, T. L., “Variables affecting the yields of fatty
esters from transesterified vegetable-oils”, Journal of the american oil chemists society, 61,1638-1643, 1984.
Freedman, B.; Butterfield, R. O. and Pryde, E. H., “Transesterification Kinetics of
Soybean Oil”, Journal of the american oil chemists society, 63, 1375-1380, 1986.
Fukuda, H.; Kondo, A. and Noda, H., ”Biodiesel Fuel Production by Transeterification of Oils.”, J. Bioscience bioengineering, vol. 92, NO. 5, 405-416, 2001.
Furuta, S., M, H. and Arata, K., “Biodiesel fuel production with solid
superacid catalysis in fixed bed reactor under atmospheric pressure”, Catalysis Communications 5, 721–723, 2004.
Haas, M. J.; Michaiski, P. J ; Runyon, S. and Nunez, A., “Scott,Production of FAME
from Acid Oil a By-product of Vegetable OilRefining.”, J. Am. Oil Chem. Soc, 80, 97-102, 2003.
Joo, K. H. and Seung, K. B., “Transesterification of vegetable oil to biodiesel using
heterogeneous base catalyst”, Catalysis today, 93, 315-320, 2004.
Kapilakarn, K. and Peugtong, A., “Comparison of Costs of Biodiesel Production from
Transesterication”, International Energy Joyrnal 8, 1-6, 2007.
Komers, K.; Tichy, J. and Skopal, F., “Ternary phase-diagram biodiesel
fuel-methanol-glycerol”, Journal fur Praktische Chemie-Chemiker-zeitung,
337, 328-331, 1995.
Kusdiana, D. and Saka, S., “Effects of water on biodiesel fuel production by
supercritical methanol treatment”, Bioresource Technology, 91, 289-295, 2004.
Kusy, P. F., “Transesterification of vegetable oils for fuels”, In Vegetable Oil Fuels Proc.
Int. Conf. on plant and Vegetable Oils as Fuels, 127-137, 1982.
Lang, X.; Dalai, A. K.; Bakhshi, N. N.; Reaney, M. J. and Hertz, P. B., “Preparation and
Characterization of Biodiesels from Various Bio-oils.Biores”, Technol, 80, 53-62, 2001.
Lee, K. T.; Foglia, T. A. and Chang, K. S., “Production of Alkyl Ester as Biodiesel from
Fractionated Lard and Restaurant Grease”, Jaocs, Vol. 79, no. 2, 2002.
Lotero, E.; Liu, Y.; Lopez, D. E.; Suwannakarn, K.; Bruce, D. A. and Goodwin, J.
G., “Synthesis of Biodiesel via Acid Catalysis”, Ind. Eng. Chem. Res, 44, 5353-5363, 2005.
Makareviciene, V.; Sendzikiene, E. and Janulis, P., “Solubility of multi-component
biodiesel fuel systems”, Bioresource Technology, 611-616, 2005.
Mazzocchia, C.; Modica, G.; Kaddouri, A. and Nannicini, R., “Fatty acid methyl
esters synthesis from triglycerides over heterogeneous catalysts in the presence of microwaves”, Compets Rendus Chimie, 601-605, 2004
Myint, L. L.; Mahmoud, M.; Halwagi, M., “Process analysis and optimization of biodiesel production from soybean oil”, Clean Techn Environ Policy, 2008.
NBB News, Average biodiesel emissions compared to conventional petro-diesel
according to U.S. EPA.
Negi, D. S.; Sobotka, F.; Kimmel, T.; Wozny, G. and Schomacker, R., “Liquid-liquid
phase equilibrium in glycerol-methanol-methyl oleate and glycerol-monoolein-methyl oleate ternary systems”, Ind. Eng. Chem. Res, 45, 3693-3696, 2006.
Noureddini, H. and Zhu, D., “Kinetics of transesterification of soybean oil”, Jaocs, Vol.74, no.11, 1997.
Romano, S., “Vegetable oils-A new alternative Vegetable Oil Fuels-Proc. INT. Conf.
on plant and Vegetable Oils as Fuels“, Fargo, N.D., 2-4 August. St. Joseph, Mich. ASAE, 106-116, 1982.
Sheehan, J.; Camobreco, V.; Duffield, J.; Graboski, M. and Shapouri, H., “An Overview of Biodiesel and Petroleum Diesel Life Cycles”, National Renewable Energy Laboratory, 580-24772., 1998.
Sonntag, N. O. V., “Structure and composition of fats and oils. Bailey’s industrial oil
and fat products”, vol. 1, 4th edition, ed. Swern, D. John Wiley and Sons, New York, 1979.
Van Gerpen, J.; Shanks, B.; Pruszko, R.; Clements, D. and Knothe, G., “Biodiesel
Production Technology”, National Renewable Energy Laboratory, 510-36244, 2004.
Van Kasteren, J. M. N. and Nisworo, A. P., “A process model to estimate the cost of
industrial scale biodiesel production from waste cooking oil by supercritical transesterification”, Resources Conservation and RecyclinG, 50, 442-458, 2007.
Shimada, Y.; Watanabe, Y. ; Samujawa, T.; Sugihara, A. ; Noda, H.; Fukuda, H. and Tominaga, Y., “Conversion of Vegetable Oil to BiodoeselUsingImmobilized Candida antarctica Lipase. Ibid.” , Vol. 76, 789-793, 1999.
Suppes, G. J.; Dasari, M. A.; Doskocil, E. J.; Mankidy, P. J. and Goff, M. J., “Transesterification of soybean oil with zeolite and metal catalysts”, Applied Catalysis A. General. 257, 213-223, 2004.
Renzo, D. F.; Danilo, D. F.; Paola, D. A. and Piero, O., “Component Distribution between Light and Heavy Phases in Biodiesel Processes”, Ind. Eng. Chem. Res. 47, 7862-7867, 2008.
XIAO, Min. and Zhong, Y. J., “Production of biodiesel using supercritical methanol technology”, 2006.
Zhang, Y.; Dube, M. A.; McLean, D. D. and Kates, M., “Biodiesel production from waste cooking oil: 1. Process design and technological assessment”, Bioresource Technology 89, 1-16, 2003.
Zhang, Y.; Dube, M. A.; McLean, D. D.and Kates, M., “Biodiesel production from waste cooking oil:2.Economic assessment and sensitivity analysis”, Bioresource Technology 90, 229-240, 2003.
Zheng, S.; Kates, M.; Dube, M. A. and McLean, D. D., “Acid-catalyzed production of biodiesel from waste frying oil”, Biomass and Bioenergy. 30, 267-272, 2006.
Zhou, H.; Lu, H. and Liang., “Solubility of multicomponent systems in the biodiesel production by transesterification of Jatropha curcas L. oil with methanol”, J.Chem. Eng., 51, 1130-1135., 2006.
丁靈、王延臻和劉晨光，“雞油製備生質柴油的研究”，中國糧油學報，第22卷第4期， 2007年。
李宗育，“利用廢棄沙拉油製造生質柴油之研究”私立高苑科技大學，碩士學位論文， 2005年。
沈胤亨，“生質柴油製程之整廠程序設計與控制”，國立臺灣大學化學工程學研究所碩士學位論文， 2008年。
巫國維，“固體催化劑生產生質柴油之研究”，國立清華大學化學工程研究所碩士論文， 2008年。
林秉賢，“廢食用油製造生質柴油(Biodiesel)-新式的生質柴油反應器”，國立清華大學化學工程研究所碩士論文， 2007年。
林昀輝、吳佩芬、盧文章、李宏台，“生質柴油的發展與推動”，工業技術研究院能源與環境研究所， 2007年。
林忠亮，方柄勳，黃冬梨，吳奇生，「大豆油生產生質柴油之生物轉酯化技術探討」，石油季刊，第四十一卷,第四期，第51-58頁， 2005年。
馬俊林、徐廣輝、郭軍和郭俊寶，“大豆酸化油製備生物柴油的研究”，可再生能源學報，第25卷第1期， 2007年。
陳介武，“生化柴油發展與趨勢”，美國黃豆協會， 2000年。
陳介武，“防制空氣污染面面觀-全球採用生質柴油，空氣清潔而保健康-”， 2005年。
陳介武，“生質柴油帶來新的低價工業原料-甘油”，美國黃豆協會， 2008年。
張傳龍、紀威、符太軍和姚亞光，“餐飲業廢油脂制取生物柴油的工藝研究”，中國糧油學報，第20卷第6期， 2005年。
張瑞玉，“由植物油生產生質柴油之製程模擬”，化工資訊與商情，2009年。
董懷仁，“廢食用油與高酸油製造生質柴油之反應參數探討”，國立清華大學化學工程研究所碩士論文， 2006年。
楊世傑，“大豆油轉酯化反應研究”，國立嘉義大學應用化學研究所碩士論文， 2007年。
劉文宗，“生質柴油發展與工業化計設”，永續產業發展，第35期， 2007年。
賴朝琴，“ 從農業廢棄物米糠生產生質柴油之研究” 國立臺灣科技大學，碩士學位論文， 2004年。
蘇有勇、張無敵、劉士清和劉偉偉，“植物油製備生質柴油的研究”，可再生能源學報，第124期， 2005年。
謝志誠，“生質柴油與石化柴油之比較”，台灣大學生物產業機電工程學系，2007。
魏益民、陳風亮、鐘耕和康立宁，“餐飲廢油脂酯化降酸工業化研究”，中國糧油學報，第22卷第5期， 2007年。