臺灣博碩士論文加值系統

廢食用油由於對環境有害，許多國家皆有立相關環保法規管制。並且由於能源的短缺，以廢食用油做為生質能源的原料已逐漸成為一個趨勢，所以廢食用油慢慢的作為生質柴油、生質汽油…等再生能源的製造來源。
目前生質柴油常使用轉酯化反應進行生產，採用鹼性觸媒進行催化，其優勢為反應時間短且有高轉化率，但若遇到使用原料含有游離脂肪酸的話會產生皂化反應，所以含有游離脂肪酸的油品需先經過酯化反應將酸轉化，再進行轉酯化反應，以避免對系統的損害。
常見的酯化反應以均相觸媒為主，如以鹽酸、硫酸…等，但生產出的產物尚需油水分離與酸鹼處理，所以出現非均相觸媒進行催化的方式，可使觸媒與產物容易分離。本研究利用模擬廢食用油流經裝有Amberlyst BD 20觸媒的觸媒連續反應器，以非均相觸媒的催化方式測定不同油料的組成(油酸、大豆沙拉油、水之間的比例)、油醇比、質量流率、溫度對酯化反應的影響，結果顯示以油醇比1：44、質量流率0.5 g/s、溫度65℃的情形下對不同的模擬廢油皆有好的效果。同時使用張之實驗數據(張筑鈞，2018)進行迴歸，尋找動力學參數，帶入Aspen Plus，進行理論值計算，以作為比較，結果顯示實驗數據與Aspen Plus模擬之趨勢結果相同。

Waste cooking oil (WCO) is harmful to our environment; thus many countries have the relevant environmental regulations. Due to the shortages of energy, using WCO as the material for green energy has become a trend. Therefore, WCO has become the source material of renewable energy, such as biodiesel, biogas, etc.
The normal way to make biodiesel is using transesterification method, catalyzed by base catalyst. The advantage of transesterification is the high conversion and short time reaction, but if there is free fatty acid (FFA) in the material, it will make saponification happen. Therefore, esterification will be used first to remove the FFA, then doing the transesterification to avoid the damage to the system.
Normally esterification is using homogeneous catalysts such as hydrochloric acid, sulfuric acid, etc. However, the product by this method need to separate the aqueous phase and oil phase, also the aqueous phase has to be neutralized by base. Therefore, heterogeneous method has become more popular for use, makes the catalyst and product to separate easily. This research using synthetic acid oil flow through the column packed with Amberlyst BD 20 catalyst in the continuous catalyst reactor. The following conditions: different composition of synthetic acid oil (different ratios of oleic acid, soybean oil, and water), different molar ratios of methanol to synthetic acid oil, different mass flow rates, and different temperatures has been tested to understand their effects on esterification. The results showed that when the molar ratio of methanol to synthetic acid oil is 44, mass flow rate is 0.5 g/s, temperature is 65℃ had the good result for the synthetic acid oils. The data of batch experiment from Chang’s thesis (Chang, 2018) is used for data regression to find kinetic parameters. A kinetic model with the regression result is then used to simulate by Aspen Plus. As a comparison, the results showed that the experimental data trends were consistent with the results simulated by Aspen Plus.

Acknowledgments i
Abstract iii
摘要 v
Table of Contents vi
List of Tables ix
List of Figures x
Chapter 1 Introduction 1
1.1 Background 1
1.2 Objectives and Scope 5
Chapter 2 Literature Review 7
2.1 Biodiesel Production Method 7
2.1.1 Microemulsion 7
2.1.2 Pyrolysis 8
2.1.3 Transesterification 9
2.1.4 Esterification 11
2.2 Waste Cooking Oil (WCO) 12
2.3 Continuous Method 14
2.4 Ion-exchange Using on Esterification 17
2.5 Kinetic Model 23
2.6 Thermal Method 24
2.7 Analysis method - Acid Value 25
Chapter 3 Experimental 27
3.1 Materials 27
3.2 Equipment and Apparatus 27
3.3 Procedure 30
3.3.1 Experimental Procedure 30
3.3.2 Analysis Procedure 31
3.4 Oleic Acid Removal and Conversion Calculation 31
Chapter 4 Results and Discussion 35
4.1 Effects of Initial Acid Value (AV0) 35
4.2 Effects of Water Content 41
4.3 Effects of Molar Ratios 47
4.4 Effects of Mass Flow Rates 49
4.5 Effects of Reaction Temperatures 51
4.6 Experiment Results Compared with Simulation 53
4.6.1 Kinetic Model and Parameters Estimation 53
4.6.2 Comparison with Aspen Plus Result 58
Chapter 5 Conclusions and Future Works 66
5.1 Conclusions 66
5.2 Future Works 67
References 68

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