以超臨界甲醇製備生質柴油之動力行為研究｜國立臺灣科技大學博碩士論文系統

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研究生：	蔡雨廷 Yu-Ting Tsai
論文名稱：	以超臨界甲醇製備生質柴油之動力行為研究 Kinetic Behavior of Biodiesel Production with Supercritical Methanol
指導教授：	李明哲 Ming-Jer Lee
口試委員:	林河木 Ho-Mu Lin 陳瑞堂 Jui-Tang Chen 李亮三 Liang-Sun Lee 李夢輝 MENG HUI, LI
學位類別：	博士 Doctor
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2011
畢業學年度：	99
語文別：	英文
論文頁數：	125
中文關鍵詞：	生質柴油、超臨界甲醇、動力
外文關鍵詞：	Biodiesel, supercritical methanol, Kinetics
相關次數：	點閱：256 下載：5
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上一筆

本研究使用連續式超臨界反應程序探討以無觸媒添加轉酯化與酯化反應製備生質柴油之的動力行為研究。在超臨界轉酯化反應的實驗，操作溫度介於553 K ∼ 593 K之間、壓力介於100 bar ∼ 250 bar之間、甲醇/葵花油的進料莫耳比從20 到 60，以及二氧化碳/甲醇的進料莫耳比為0.1下。實驗結果顯示反應速率與生質柴油產率隨反應溫度的增加而提高，但對壓力並不敏感。生質柴油產率會隨之增大而提高，但大於25以上，其產率趨近於一定值。至於二氧化碳的添加反而稀釋了進料濃度，造成生質柴油產率的下降。
在超臨界酯化反應的實驗，操作溫度介於493 K ∼ 533 K間、壓力為100 bar、甲醇/油酸的進料莫耳比介於2 到 5間。由實驗結果得知，油酸的轉化率隨溫度與進料比的提高而增加。當酯化反應操作於甲醇之超臨界條件時，可顯著提昇反應速率。
本研究的超臨界轉酯化與超臨界酯化動力數據中，分別以冪次方動力模式關聯，並求得模式中的動力參數值。關聯結果顯示這些動力模式均能合理描述超臨界轉酯化與超臨界酯化的反應動力行為。

The kinetic behavior of biodiesel production from non-catalytic transesterification and esterification with a continuous supercritical process was investigated in this study. In transesterification reaction, the biodiesel was produced from refined sunflower oil and methanol in the presence of carbon dioxide at the conditions of (the molar ratios of methanol to triglyceride) from 20 to 60 and (the molar ratio of CO2 to methanol ) = 0.1, temperatures from 553 K to 593 K, and pressures from 100 bar to 250 bar. The reaction rate and FAME yield increase with increasing reaction temperature and those appear to be insensitive to pressure. The FAME yield increases with , but it reaches a constant as greater than 25. It is also found that the FAME yield decreases with the addition of carbon dioxide due to the dilution effect.
In esterification reaction, the biodiesel was synthesized from the oleic acid and methanol. The experimental runs were conducted at (the molar ratios of methanol to oleic acid) from 2 to 5, temperatures from 493 K to 533 K, and under 100 bar. The conversion of oleic acid increases with increasing reaction temperature and feed molar ratio of . The reaction rate was significantly enhanced as the esterification was conducted at the supercritical condition of methanol.
The kinetic data of both transesterification and esterification were correlated with power law models to determine the kinetic parameters. The correlated results show that the models represent well the kinetic behavior of the transesterification and the esterification reactions for biodiesel production.

Table of Contents
	Pages
English Abstract	I
Chinese Abstract	III
Acknowledgement	IV
Table of Contents	V
List of Figures	VIII
List of Tables	XI

Chapter 1   Introduction
1-1	The development of biodiesel production technology	1
1-2	Literature review	2
	1-2-1	Homogeneous catalyst	2
	1-2-2	Heterogeneous catalyst	3
	1-2-3	Non-catalytic reaction	5
1-3	The addition of co-solvent	9
1-4	Outline of this dissertation	10
Chapter 2   Biodiesel production with a continuous supercritical transesterification in the presence of with CO2	18
2-1	Experimental section	18
	2-1-1	Materials	18
	2-1-2	Experimental conditions	19
	2-1-3	Experimental procedure	19
	2-1-4	FAME analysis	20
	2-1-5	Determination of FAMEs	21
	2-1-6	Validation with literature data	21
2-2	Results and discussion	22
	2-2-1	Pressure effect	23
	2-2-2	Feed composition effect	23
	2-2-3	Temperature effect	23
	2-2-4	Effect of the presence of carbon dioxide 	24
2-3	Correlation of kinetic data	24
2-4	Conclusions	26
Chapter 3   Non-catalytic esterification of oleic acid with methanol at elevated pressure	41
3-1	Experimental section	41
	3-1-1	Materials	41
	3-1-2	Experimental conditions	42
	3-1-3	Experimental procedure	42
	3-1-4	Composition analysis	43
	3-1-5	GC calibration	43
3-2	Results and Discussion	44
	3-2-1	Feed composition effect	45
	3-2-2	Temperature effect	45
	3-2-3	The effect of phase of methanol	46
3-3	Correlation of kinetic data	46
3-4	Conclusions	48
Chapter 4   Conclusions	60
Nomenclature and units	62
References	64
Appendix I  Kinetics of catalytic esterification of acetic acid with methanol over Amberlyst 36	72
Appendix II  Kinetics of catalytic esterification of proponic acid with methanol over Amberlyst 36	99
作者簡介	124





List of Figures
Figure		Pages
1-1     Mechanism of transesterification reaction	15
1-2     Transesterification in supercritical methanol process by using a batch reactor	16
1-3     Two-step process for biodiesel production developed by Minami and Saka (2006)	16
1-4     Two-step process for biodiesel production developed by D’Ippolito et al. (2007)	17
2-1     The schematic diagram of the continuous supercritical transesterification system	32
2-2     A chromatogram of methyl esters	33
2-3     The calibration of methyl palmitate using heptadecanoic acid as an internal standard	33
2-4     The calibration of methyl stearate using heptadecanoic acid as an internal standard	34
2-5     The calibration of methyl oleate using heptadecanoic acid as an internal standard	34
2-6     The calibration of methyl linoleate using heptadecanoic acid as an internal standard	35
2-7     The calibration of methyl linolenate using heptadecanoic acid as an internal standard	35
2-8     Pressure effect of FAME yield ( = 42 ,  = 0.1, 553 K andτ≈ 30 min)	36
2-9     Feed composition ( ) effect on FAME yield ( = 0.1, 553 K ,and 100 bar)	37
2-10    Kinetic behavior of the transesterification at different reaction temperatures ( = 25,  = 0.1, and 100 bar )
38
2-11    The comparison of correlated FAME yields with experimental values	39
2-12    Rate constants of forward and backward reactions at different temperatures	40
3-1     Schematic diagram of the experimental apparatus	53
3-2     GC calibration for oleic acid using heptadecanoic acid as an  internal standard	54
3-3     Correlation of oleic acid density with temperature	54
3-4     Kinetic behavior of esterification of oleic acid with methanol at 513 K and 100 bar under different feed compositions	55
3-5     Kinetic behavior of the esterification of oleic acid with methanol at  = 5 and 100 bar under different reaction temperatures
56
3-6     Comparison of correlated results with experimental values at 100 bar and  = 5 under different reaction temperatures
57
3-7     Comparison of correlated results with experimental values at 513 K and 100 bar under different feed compositions	58
3-8     Rate constants of forward and backward reactions at different temperatures	59
AI-1    Schematic diagram of the kinetic experimental apparatus	87
AI-2    Schematic diagram of the adsorption experimental apparatus	88
AI-3    Kinetic behavior of the esterification of acetic acid with methanol at  = 3 under different reaction temperatures
89
AI-4    Kinetic behavior of the esterification of acetic acid with methanol at 323.15 K under different feed compositions	90
AI-5    Comparison of conversion of acetic acid by using different catalyst loadings and sizes of catalyst beads at 323.15 K and  = 3
91
AI-6    Results of adsorption experiments for the binary systems of acetic acid (1) + methyl acetate (2) at 328.15 K over Amberlyst 36	92
AI-7    Results of adsorption experiments for the binary systems of methanol (1) + methyl acetate (2) at 328.15 K over Amberlyst 36	93
AI-8    Results of adsorption experiments for the binary systems of water (1) + methanol (2) at 333.15 K over Amberlyst 36	94
AII-1   Kinetic behavior of the esterification of propionic acid with methanol at  = 3 and under different reaction temperatures
113
AII-2   Kinetic behavior of the esterification of propionic acid with methanol at 323.15 K and under different feed compositions	114
AII-3   Comparison of conversion of propionic acid by using different catalyst loadings and sizes of catalyst beads at 323.15 K and   = 3	115
AII-4   Results of adsorption experiments for binary systems of                      methyl propionate (1) + propionic acid (2) at 333.15 K over Amberlyst 36	116
AII-5   Results of adsorption experiments for binary systems of methyl propionate (1) + methanol (2) at 333.15 K over Amberlyst 36	117
AII-6   Results of adsorption experiments for binary systems of water (1) + methanol (2) at 333.15 K over Amberlyst 36	118
AII-7   Comparison of calculated results from different models with experimental values at 323.15 K and   = 3
119














List of Tables
Table		Pages
1-1    Values for the American Society for Testing and Materials (ASTM) standards of maximum allowed quantities in diesel and biodiesle	12
1-2    Comparison of characteristics of between the catalytic and the supercritical methanol methods for biodiesel production	13
1-3    Critical temperatures and critical pressures of various alcohols	14
2-1    The validation of experimental apparatus	28
2-2    The experimental data of the transesterification of sunflower oil and methanol with CO2 as a co-solvent in supercritical process	29
2-3    Correlated results of the kinetic data	31
3-1    Fatty acid compositions of vegetable oil samples	49
3-2    The density of methanol at various temperatures and a fixed pressure	50
3-3    Experimental results of the esterification of oleic acid with methanol	51
3-4    Correlated results of the kinetic data of esterification of oleic acid with methanol	52
AI-1   Experimental results of the esterification of acetic acid with methanol	83
AI-2   Parameters of the NRTL model for the investigated system	84
AI-3   Correlated results of the adsorption data	85
AI-4   Correlated results of kinetic data	86
AII-1   Experimental conditions and results of esterification of propionic acid with methanol	109
AII-2   Parameters of the NRTL for mixtures containing propionic acid (1), methanol (2), methyl propionate (3), and water (4)	110
AII-3  Correlated results of adsorption data	111
AII-4   Correlated results of kinetics data	112

                                

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