臺灣博碩士論文加值系統

生質柴油具有低污染及永續再生之優點，一般原料來源為動植物油脂，例如:大豆、廢油和油菜籽可再生利用作為原料，利用動植物油脂加上低分子的醇類經由催化劑轉酯化過程即可得到生質柴油。
本研究使用CHEMCAD®化工製程軟體，台灣生質柴油標準CNS-15072為規範，以三油酸甘油酯（C57H104O6）代表大豆油為原料，進行（1）典型雙反應器系統、（2）甘油相逆迴流雙反應器系統、（3）甘油相自迴流雙反應器系統、（4）甘油相自迴流單反應器系統，四個鹼性反應架構之生質柴油製程探討。分析結果以甘油相迴流單反應器系統成本最低，而雙反應器系統中則以甘油相自迴流雙反應器系統成本最低，較典型雙反應器系統低17%。
本研究以熱力學模式UNIQUAC迴歸生質柴油/甘油/甲醇液液平衡，與預測之UNIFAC模式比較，因UNIFAC模式計算之沉降槽甲醇溶解度較低，由UNIFAC預測模擬之沉降槽體積較大，而所需之醇油比亦較高。

Biodiesel is one of the mostly used renewable fuels in the world, which has the advantages of low pollutant emissions and sustainability. The feedstocks for biodiesel production can be animal fats or vegetable oils such as tallow, waste cooking oil, soybean oil and rapeseed oil. Biodiesel can be produced from these fats or oils with alcohol through transesterification reaction.
In this study, the commercial simulator CHEMCAD® is used to analyze the alkaline-catalyzed biodiesel processes. Four alkaline-catalyzed processes were analyzed: (1) traditional two-reactor process (2) glycerol phase recycle two-reactor process (3) glycerol phase self-recycle two-reactor process (4) glycerol phase recycle one-reactor process. The unit cost of biodiesel for glycerol phase recycle one-reactor process is the lowest. Among the two-reactor processes, the cost for the glycerol phase self-recycle two-reactor process is the lowest, which is 17% lower than the traditional two-reactor process.
The liquid-liquid equilibrium of biodiesel/glycerol/methanol is regressed from literature experimental data by UNIQUAC model in this study. Comparing the QNIQUAC and predictive UNIFAC models, the UNFAC model predicts larger decanter and higher alcohol to oil ratio.

摘 要 i
Abstract ii
誌 謝 iii
目 錄 iv
圖 目 錄 vi
表 目 錄 vii
第一章 緒論 1
1-1前言 1
1-2研究動機與目的 4
第二章 文獻回顧 5
2-1生質柴油料源 5
2-2生質柴油製程相關研究 8
2-2-1鹼性觸媒 8
2-2-2酸性觸媒 10
2-2-3超臨界流體反應 11
2-2-4酵素催化反應 12
2-2-5固體觸媒製程 13
2-3生質柴油規範 15
2-4反應動力學 18
2-5熱力學模式 23
2-6生質柴油製程分析 24
第三章 生質柴油製程模擬 27
3-1系統成分 27
3-2轉酯化反應動力學 28
3-3熱力學模式 29
3-4反應器系統分析 32
3-4-1單反應器系統(I) 32
3-4-2單反應器系統(II) 33
3-4-3雙反應器系統(I) 35
3-4-4雙反應器系統(II) 36
3-4-5雙反應器系統(III) 37
3-5反應器系統比較 39
3-6-1設計基準 40
3-6-2總年成本分析 41
3-6-3生質柴油製程設計原則 41
3-6-4單反應器系統(II) 42
3-6-5雙反應器系統(I) 44
3-6-6雙反應器系統(II) 46
3-6-7雙反應器系統(III) 48
第四章 結果與討論 50
4-1各製程之分析比較 50
4-2製程設計熱力學比較 54
第五章 結論 55
參考文獻 56
附錄A 計算TAC使用之公式 61
附錄B 反應系統質能平衡結果 64
附錄C 生質柴油檢驗方法 78

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