本論文係利用兩階段酯化/轉酯化系統轉製廢食用油成生質柴油之程序合成與設計。第一階段為酯化/轉酯化製程設計並採用 H2SO4為酸性觸媒，第二階段為轉酯化製程設計並採用NaOH為鹼性觸媒。廢食用油主要含進料油酯與游離酯肪酸；吾人以三酸甘油酯代表進料油酯並以十八烯酸代表游離酯肪酸。研究中並結合狹點技術與換熱器網路合成原理，比較熱能整合前後的能源消耗並計算其化石能源之比值。
    論文中主要使用兩套程序軟體：Aspen Plus主要用來進行程序設計與合成；SuperTarget則用來進行程序之狹點分析及換熱器網路合成。

In the thesis, we present a process synthesis and design for the production of biodiesel from waste cooking oil by utilizing two-stage transesterification processes.  While in the first stage esterification/transesterification process design was carried out using H2SO4 as the acid catalyst, in the second stage transesterification process design was carried out using NaOH as the alkaline catalyst.  The waste cooking oil consists mainly of feeding oil and free fatty acid.  In this work, we used triglyceride to represent the feeding oil and oleic acid to represent the free fatty acid.  In the study, we also combine the pinch technology with the base-case design for heat exchanger network synthesis so as to compare the energy consumptions and determine the fossil energy ratio with/without heat integration.
    Two kinds of software were utilized in the research: Aspen Plus was mainly used for the process simulation; SuperTarget was used to carry out the pinch analysis and the synthesis of heat exchanger network.

目錄
中文摘要……………………………….……………………. i
英文摘要………………………………………………… ...ii 
目錄…………….…………………………………......…iii
圖目錄…………….………………………………….......vi
表目錄…………….………………………………………… ix
第一章	緒論……………………………………………....1
1.1	 研究動機……………………………………….…1
1.1.1生質柴油之製造方法……………………………………2
1.1.2 生質柴油在工業上製備……………………………...5
1.2	研究目的與方法………………………………....6
第二章	理論基礎……………………………………………11
2.1 程序合成與設計……………………………………….…11
2.1.1程序合成之經驗法則……………………………………11
2.1.2洋蔥模式…………………………………………………12
2.1.3 程序合成模式……………………………………………12
2.1.4 程序的核心 － 反應器…………………………………13
2.1.5 第二層 － 分離系統……………………………………14
2.1.6 第三層 － 迴流結構……………………………………14
2.1.7 第四層 － 換熱器網路…………………………………15
2.1.8 最外層 － 公用設施……………………………………15
2.2 狹點技術在能源減碳上之應用……………………………16
2.2.1 製程模擬…………………………………………………17
2.2.2 換熱器網路設計問題的定義……………………………21
2.2.3 換熱器網路設計之重要概念……………………………21
2.2.4 熱回收狹點之概念………………………………………22
2.2.5 換熱器網路目標值之建立………………………………22
2.2.6 狹點技術………………………...………………….…23
2.2.7 數據擷取…………..……………………………………24
2.2.8 狹點分析………………………………………….…….26
2.2.9 換熱器網路合成……………………………………..…31
2.2.10 選擇可行方案……………………………………….…32
2.3 熱能整合之範例……………………………………………32
2.3.1 數據擷取……………………………………………..…34
2.3.2 狹點分析…………………………………………………35
2.3.3 換熱器網路合成…………………………………………41
2.3.4 換熱器網路組態設計……………………………………41
第三章	廢食用油轉製生質柴油之製程設計……………….46
3.1 製程描述……………………………………………………46
3.1.1 第一階段之酯化/轉酯化反應……………………..……46
3.1.2 第二階段之轉酯化反應…………………………………46
3.1.3 甲醇純化………………………………………………..48
3.1.4 轉酯化反應……………………………………………..48
3.1.5 甲醇回收塔……………………………………………..49
3.1.6 水洗滌塔…………………………………………………49
3.1.7 生質柴油之熱值…………………………………………50
3.1.8 生質柴油之化石能源比…………………………………56
3.2 製程模擬……………………………………………………57
第四章	廢食用油轉製生質柴油之熱能整合…………….…75
4.1 數據擷取……………………………………………………75
4.2 狹點分析……………………………………………………87
4.3 換熱器網路合成……………………………………………88
4.4 換熱器網路組態設計……………………..………………121
第五章	結論與建議……………………………………….…123
第六章	參考文獻…………………………………………….126
 
圖目錄
圖1.1、廢食用油轉製生質柴油製程之方塊流程圖………….…7
圖2.1、程序設計之洋蔥模式圖…………………………………13
圖2.2、整體分離系統組合圖…………………………………..15
圖2.3、製程模擬之結構圖………………………………………18
圖2.4、T-Q圖之線性分段…………………………………….…25
圖2.5、單成份系統之相變化圖 (假設ΔT=1°C)……………….25
圖2.6、最佳操作點之示意圖……………………………………26
圖2.7、ΔTmin改變與驅動力關係示意圖…………………….…28
圖2.8、複合曲線建立示意圖……………………………………29
圖2.9、熱量串級示意圖…………………………………………31
圖2.10、未經熱能整合之程序流程範例…………………….…33
圖2.11、範例子中ΔTmin =10°C時之冷、熱複合曲線……..…36
圖2.12、範例子中ΔTmin =20°C時之冷、熱複合曲線…………36
圖2.13、範例中之熱複合曲線……………………………….…37
圖2.14、範例中之冷複合曲線……………………….………..38
圖2.15、範例中之總複合曲線圖…………………………….…39
圖2.16、範例中之冷熱物流網格圖…………………..…….…40
圖2.17、狹點上方配對(a)錯誤之配對CPHot≧CPCold………..42
圖2.18、狹點上方配對(b)正確之配對 CPHot≦CPCold…….…42
圖2.19、狹點下方之配對………………………………………..43
圖2.20、Smith範例完成之換熱器網路網格圖…………..….…44
圖2.21、經熱整合之換熱器網路組態圖…………………………45
圖3.1、廢食用油轉製生質柴油製程之程序流程圖…………….47
圖3.2、Aspen Plus中熱值之計算步驟………………………….51
圖3.3、建立蒸餾塔壓力和冷凝器種類的演算法..…………...59
圖3.4、廢食用油轉製生質柴油製程之模擬流程圖………….…65
圖4.1、廢食用油轉製生質柴油製程中換熱器E-101之T-Q圖….75
圖4.2、廢食用油轉製生質柴油製程中換熱器E-102之T-Q圖……76
圖4.3、廢食用油轉製生質柴油製程中換熱器E-103之T-Q圖……76
圖4.4、廢食用油轉製生質柴油製程中換熱器E-104之T-Q圖…….77
圖4.5、廢食用油轉製生質柴油製程中換熱器E-105之T-Q圖…….77
圖4.6、廢食用油轉製生質柴油製程中換熱器E-106之T-Q圖…….78
圖4.7、廢食用油轉製生質柴油製程中換熱器E-107之T-Q圖…….78
圖4.8、廢食用油轉製生質柴油製程中換熱器E-108之T-Q圖…….79
圖4.9、廢食用油轉製生質柴油製程中換熱器E-109之T-Q圖…….79
圖4.10、廢食用油轉製生質柴油製程中換熱器E-110之T-Q圖……80
圖4.11、廢食用油轉製生質柴油製程中換熱器E-111之T-Q圖…….80
圖4.12、廢食用油轉製生質柴油製程中換熱器E-112之T-Q圖….…81
圖4.13、廢食用油轉製生質柴油製程中換熱器E-113之T-Q圖…...81
圖4.14、廢食用油轉製生質柴油製程中換熱器E-114之T-Q圖…….82
圖4.15、廢食用油轉製生質柴油製程中換熱器E-115之T-Q圖….…82
圖4.16、ΔTmin=5°C時，廢食用油轉製生質柴油製程之複合曲線圖
......................................................90
圖4.17、ΔTmin=10°C時，廢食用油轉製生質柴油製程之複合曲線圖.......................................................91
圖4.18、ΔTmin=15°C時，廢食用油轉製生質柴油製程之複合曲線圖.......................................................92
圖4.19、ΔTmin=20°C時，廢食用油轉製生質柴油製程之複合曲線圖.......................................................93
圖4.20、ΔTmin=25°C時，廢食用油轉製生質柴油製程之複合曲線圖......................................................94
圖4.21、廢食用油轉製生質柴油之製程於ΔTmin = 5oC時換熱器網路合成之網格圖……………………………………………..........96
圖4.22、廢食用油轉製生質柴油之製程於ΔTmin = 10°C時換熱器網路合成之網格圖…………………………………………….....101
圖4.23、廢食用油轉製生質柴油之製程於ΔTmin = 15°C時換熱器網路合成之網格圖……………………………………….……....106
圖4.24、廢食用油轉製生質柴油之製程於ΔTmin = 20°C時換熱器網路合成之網格圖………………………………………….....…111
圖4.25、廢食用油轉製生質柴油之製程於ΔTmin = 25°C時換熱器網路合成之網格圖…………………………………………….....116
圖4.26 熱能整合 (ΔTmin=10°C) 後之廢食用油轉製生質柴油最後組態圖……………………………………………………….......122
 
表目錄
表1.1、ASTM (美國材料測試協會) 生質柴油B100 燃料規範.…9
表2.1、Aspen Plus軟體中EOS/GE模式範例……………….....20
表2.2、溫度區間內之熱平衡表………………………………….30
表2.3、程序之主要冷熱物流資料表………………………….34
表3.1、常用燃料之熱值………………………………………50
表3.2、各蒸餾塔之設定條件…………………………………58
表3.3、各蒸餾塔“Design Specs”之設定條件……………61
表3.4、熱交換器之設定………………………………………62
表3.5、泵浦之設定……………………………………..….63
表3.6、廢食用油轉製生質柴油製程之物流資料表…………66
表4.1、廢食用油轉製生質柴油之換熱器資料表……………85
表4.2、廢食用油轉製生質柴油之冷、熱物流資料表………89
表4.3、不同最小趨近溫度之冷、熱公用設施比較表………95
表4.4、不同趨近溫度下所節省之冷、熱公用設施百分比…95
表4.5、ΔTmin = 5°C之換熱器網路配對資料表……………..97
表4.6、ΔTmin = 10°C之換熱器網路配對資料表……………..102
表4.7、ΔTmin = 15°C之換熱器網路配對資料表…………….107
表4.8、ΔTmin = 20°C之換熱器網路配對資料表………………112
表4.9、ΔTmin = 25°C之換熱器網路配對資料表………………117

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