超臨界流體轉酯化反應製備生質柴油｜國立清華大學博碩士論文庫

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研究生：	洪英哲 Hung, Ing-Zhe
論文名稱：	超臨界流體轉酯化反應製備生質柴油 Preparation of Biodiesel by Transesterification Using Supercritical Fluid
指導教授：	談駿嵩 Tan, Chung-Sung
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2010
畢業學年度：	98
語文別：	中文
論文頁數：	75
中文關鍵詞：	超臨界流體、轉酯化反應、生質柴油
相關次數：	點閱：4 下載：0
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摘要
由於商業鹼製程在轉酯化反應的過程中，會受限於原料中的水分及游離脂肪酸，而產生皂化作用，使產率下降；且於製程中需加入液體觸媒，而使得轉酯化反應後的產物須經過水洗中和鹼液，所產生的廢液會增加分離純化的困難度並造成環境的污染。另一方面，轉酯化的原料大多是由動植物油脂而來，因此若要大量發展生質柴油，勢必會產生原料缺乏的情況，所以須選擇無競爭性的油脂，以減低原物料缺乏的風險並維持穩定的供應鏈。

為改善鹼製程的缺失，本研究以不可食用的麻瘋油與甲醇為原料，在超臨界甲醇的條件下，於連續式管狀反應器中進行轉酯化反應，且亦於反應器中填入固體觸媒及添加共溶劑，促進醇油間的接觸及混合，以減少製程的能耗並加速轉酯化反應的進行。藉由獲得轉酯化反應的產率，可得到最適操作條件；此外，亦可求出動力式參數，以作為日後放大設計之依據。

實驗結果顯示，在操作溫度為280℃、壓力為2000 psi、醇油莫耳比為24及滯留時間為20分鐘時，以填充氧化錳觸媒進行轉酯化反應；與未填充觸媒時相比，甲基酯產率由20%左右，大幅提升至99%以上，且在觸媒作用下，可縮短滯留時間於11分鐘，即可達到穩定的高產率；另一方面，添加乙醚共溶劑於轉酯化系統，在操作壓力為2000 psi、醇油莫耳比為12、滯留時間為5.5分鐘，乙醚與甲醇的莫耳比為0.1下，發現在溫度260℃以上，甲基酯產率有些微的成長，與觸媒催化的效果相比，共溶劑促進反應速率的影響是非常微弱的。

在動力學方面，藉由一階線性方程式進行轉酯化反應之擬合結果，於填充觸媒下，反應的活化能由5686 (J/mol K)降至3063(J/molK)，有明顯的下降；而由求得之指前因子及活化能代回反應之動力式，可得知於填充觸媒下之轉酯化反應動力式為-r(TG)=185 exp((-3063)/RT)C_A^ 。

摘要    I
目錄    III
表目錄    V
圖目錄    VI
壹、緒論    1

貳、文獻回顧    3
2-1  原料油性質及應用    3
     2-1-1  原料油脂之組成    3
     2-1-2  原料油之選擇    3
     2-1-3  原料油之應用    4
2-2  轉酯化反應    5
         2-2-1  鹼催化法    7
         2-2-2  超臨界流體法    8
2-3  轉酯化反應之動力學研究    11
     2-3-1  轉酯化反應之反應機構    11
     2-3-2  轉酯化反應相變化    15
    2-4  影響轉酯化反應之條件因素    16
         2-4-1  觸媒    16
2-4-2  溫度    17
2-3-3  壓力    19
2-3-4  醇油莫耳比    19
2-3-5  滯留時間    20
2-3-6  共溶劑    20
    2-5  填充床反應器設計    31
  2-5-1  壓力降效應    31
2-5-2  管壁渠道效應    32
  2-5-3  床體孔隙度效應    32

參、實驗部分    33
3-1  實驗流程及操作說明    33
3-1-1  進料油脂之前處理    33
3-1-2  轉酯化反應步驟    35
  3-1-3  反應器設計    38
3-1-4  產物純化及分析    39
3-2  實驗儀器    39
3-3  實驗藥品    41

肆、結果與討論    43
    4-1  油脂性質分析    43
    4-2  連續式轉酯化系統(超臨界流體製程)    46
         4-2-1  填充管表面活性衰退現象    46
         4-2-2  觸媒效應    47
         4-2-3  溫度效應    48
         4-2-4  壓力效應    49
         4-2-5  醇油莫耳比效應    51
         4-2-6  滯留時間效應    52
         4-2-7  原料油性質影響    53
         4-2-8  共溶劑效應    54
    4-3  批次轉酯化系統(鹼催化製程)    55
         4-3-1  醇油比效應    55
         4-3-2  觸媒量效應    56
         4-3-3  原料油性質影響    58
    4-4  鹼製程與超臨界製程之對比    59
    4-5  轉酯化反應之動力式    61
         4-5-1  轉化率對反應時間之影響    61
         4-5-2  反應之活化能對比    64

伍、結論    65

參考文獻    67
附錄    73
附錄一  生質柴油性質說明    73
附錄二  美國ASTM 生質柴油規範      74
附錄三  歐盟生質柴油規範     75

                                

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經濟部標準檢驗局,中華民國國家標準CNS3648食用油脂檢驗法-皂化價測定.

經濟部標準檢驗局,中華民國國家標準CNS3647食用油脂檢驗法-酸價測定.

江建忠,利用超臨界流體技術製備生質柴油之研究,碩士論文,國立清華大學, 2008.

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