臺灣博碩士論文加值系統

本研究探討大豆油轉製成生質柴油(Biodiesel)的新技術開發，應用超重力旋轉填充反應器(High-gravity rotating packed bed)的微觀混合技術(Micromixing)來突破傳統廢食用油轉製成生質柴油的反應瓶頸，此新穎技術將可提高生質柴油的生產效率及降低生產時所需使用的能量，將同時達到解決廢棄食用油所衍生的環境污染問題，與得到對環境更潔淨、永續、及友善的綠色能源。本研究第一部份利用大豆油來代替廢食用油並結合均相觸媒，在超重旋轉填充反應器內進行轉酯化程序。研究參數包括：甲醇與大豆油的莫耳比、反應溫度、液體流量、超重力反應器旋轉速度、及觸媒含量。在本研究實驗情況下，結果顯示對於各個參數最適化操作條件為甲醇與大豆油的莫耳比為6：1、大豆油流量為250 mL/min、反應溫度為60.8oC、及觸媒含量為3% w/w(基於大豆油的重量)、與反應器旋轉速度為900 rpm時為最佳操作條件，能增加脂肪酸甲基酯產生率(Yield of fatty acid methyl esters, YFAME)。本研究將所有參數同時調整至先前測試之最適化條件後，可以得到YFAME為96.3%與脂肪酸甲基酯的莫耳產率(Productivity of fatty acid methyl esters, PFAME)為0.695 mol/min。第二部分將製備K2O/Al2O3異相觸媒並分析觸媒之特性，再以異相觸媒填充在超重力旋轉填充器的填充床內，進行大豆油的轉酯化實驗。研究參數包括：甲醇與大豆油的莫耳比、超重力反應器旋轉速度、反應溫度、及觸媒填充重量。結果顯示在甲醇與大豆油的莫耳比由6：1提升到24:1會使反應達到平衡的時間縮短。異相觸媒的填充量由59.2 g提升至118.4 g也會使反應達到平衡的時間縮短，而再增加填充觸媒的量對於達到反應平衡的時間並無顯著縮短的現象。增加反應的溫度由30oC提高到60oC亦會使反應達到平衡的時間明顯縮短。本研究實驗在操作條件為甲醇與大豆油的莫耳比為24：1、反應溫度為60oC、及觸媒填充量為177.6 g、反應器旋轉速度為900 rpm、與迴流量為250 mL/min，在反應時間為60 min下脂肪酸甲基酯的產生率就可以達到96.4%。

This study investigates the new technology for the synthesis of biodiesel from the soybean oil with the high-gravity rotating packed bed (RPB). Biodiesel is used as alternative of diesel fuel because of its advantages in reducing the air pollution. However, the insoluble property of methanol in oil phase results in the slow reaction rate of transesterification. The biodiesel productivity in the continuous processes is usually limited due to the necessary retention time for the requirement of conversion degree. A RPB has been employed as the mass transfer device and micromixing reactor from 1980s. The flowing liquids in the RPB will form the thin liquid film on the packing materials due to the high centrifugal force. Here the RPB is applied as the transesterification reactor to transfer oil and methanol into biodiesel (Free acid methyl esters, FAME) and glycerol. The RPB, which provides high gravitational force by adjusting the rotational speed, is taken as a novel reactor owing to its high mixing efficiency. It has high potential to improve the biodiesel productivity or reduce the reactor volume by applying a RPB. The yield (YFAME) and productivity (PFAME) of fatty acid methyl esters are employed as the performance indexes of the biodiesel production. The effects of the operation conditions on the performance of the biodiesel production in the RPB system are examined. The value of YFAME significantly increases with the increase of temperature and catalyst dosage, while would be greatest at the certain values of the oil flow rate, rotating speed, and mole ratio of soybean to methanol. Furthermore, the highly potential of the RPB system for the continuous manufacture of biodiesel has been demonstrated in comparison of the results of YFAME and PFAME with the previous literatures. In the experimental conditions of the present work, the YFAME and PFAME can reach 96.3% and 0.695 mol/min, respectively.
In the second part, the heterogeneous K2O/Al2O3 catalysts are prepared and packed in the circulating RPB reactor to proceed the transesterification reaction of the soybean oil. As a result, the time required to reach the equilibrium decreases with the increasing molar ratio of methanol to soybean oil from 6 to 24. The reaction rate of the transesterification increases with the packed amount of the K2O/Al2O3 catalysts from 59.2 to 118.4 g. However the amount of the K2O/Al2O3 catalysts increases to 177.6 g showing the slight enhancement on the transesterification conversion. On the other hand, the increase of temperature in the RPB reactor remarkably increases the transesterification rate. In the condition of molar ratio of the methanol to soybean oil of 24, reaction temperature of 60oC, catalyst amount of 177.6 g, rotating speed of 900 rpm, and circulating flow rate of 250 mL/min, the transesterification coversion can reach 96.4% at reaction time of 60 min.

中文摘要 I
Abstract II
目 錄 IV
表目錄 VII
圖目錄 VIII
符號說明 XI
第一章 緒論 1
1.1 前言 1
1.2 研究目的 3
第二章 文獻回顧 4
2.1 生質柴油製造基本原理及發展現況 4
2.1.1 均相觸媒轉酯化程序 6
2.1.2 異相觸媒轉酯化程序 8
2.1.3 轉酯化反應器的種類與反應動力學 10
2.1.4 生質柴油發展現況 12
2.2 超重力旋轉填充床之原理及應用 20
2.2.1 超重力技術之發展 20
2.2.2 超重力旋轉填充床之構造及原理 21
2.2.3 超重力旋轉填充床之特性及其應用 22
第三章 儀器設備與研究方法 24
3.1 實驗藥品與儀器 24
3.1.1 實驗藥品 24
3.1.2 實驗儀器 25
3.2 實驗分析方法 27
3.2.1 以核磁共振儀分析生質柴油產率之方法 27
3.2.2 以高效能液態層析儀分析生質柴油產率及比例之方法 27
3.3 均相觸媒轉酯化程序實驗 28
3.3.1 批式均相觸媒攪拌槽系統 28
3.3.2 連續式均相觸媒超重力旋轉填充床系統 28
3.4 異相觸媒轉酯化程序實驗 29
3.4.1 異相觸媒之製備 29
3.4.2 觸媒清洗方式 29
3.4.3 批次循環式異像觸媒填充床系統 29
第四章 結果與討論 31
4.1 批式均相觸媒轉酯化系統 31
4.1.1 批式轉酯化反應系統中YFAME的討論 31
4.2 連續式均相觸媒轉酯化系統 32
4.2.1 超重力旋轉填充床系統操作條件之影響 32
4.2.2 超重力旋轉填充床系統之條件最佳化及與文獻比較 34
4.3 異相觸媒之特性分析 36
4.3.1 異相觸媒特性分析 36
4.3.2 清洗方式對YFAME的影響 36
4.4 批式液體循環式異相觸媒旋轉填充床系統 37
4.4.1 nM/nO對批次循環式異相觸媒旋轉填充床系統YFAME之影響 37
4.4.2 T對批次循環式異相觸媒旋轉填充床系統YFAME之影響 37
4.4.3 Wcat對批次循環式異相觸媒旋轉填充床系統YFAME之影響 38
4.4.4 ω對批次循環式異相觸媒旋轉填充床系統YFAME之影響 38
第五章 結論與建議 39
5.1 結論 39
5.2建議 40
参考文獻 81
附錄A. 樣品分析前處理方法與分析方法 88
A.1 文獻回顧 88
A.2 分析方法 88
A.3 批式轉酯化反應系統中樣品分析前處理方式討論 90
A.4 連續式轉酯化系統中樣品分析前處理方式討論 91
A.5 參考文獻 98
附錄B. 流量計校正 99
B.1 齒輪式流量計校正曲線 99
B.2 液體流量計校正曲線 100
附錄C. 溫度計校正 101
C.1 溫度計(一) 101
C.2 溫度計(二) 102
C.3 溫度計(三) 103
附錄D. HPLC標準品檢量線 104
D.1 MP標準品檢量線 104
D.2 MS標準品檢量線 105
D.3 MO標準品檢量線 106
D.4 ML標準品檢量線 107
D.5 MLn標準品檢量線 108
附錄E. 比較1H NMR400與1H NMR500分析出的產率 109
附錄F. 觸媒耐用度實驗 110
F.1 實驗步驟 110
F.2 實驗結果 110
附錄G. XRF分析數據 117
附錄H. TGA數據 128

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