臺灣博碩士論文加值系統

酒精汽油為生質酒精添加在石化汽油中，可以取代高污染的含鉛汽油作為替代能源，但添加在汽油中的酒精其含水量必須小於0.5wt%，若水含量超過0.5wt%現有的引擎就必須有所調整。目前工業上大多以分子篩3A當作選擇性吸附材，由於其吸附選擇性及再生效率較差，所以近年來有些學者開始利用澱粉等材料來當作吸附材。未經處理的澱粉吸附材在吸附水分子後，膨潤及糊化等問題造成澱粉再生後的吸附力大幅下降，因此，本研究將澱粉固定化在矽膠基材上，以求解決澱粉在吸附上所遇到的問題。本研究利用Sol-Gel法成功將澱粉固定化在矽膠基材上，利用能量散佈光譜儀 (Energy - dispersive X-ray, EDX)分析證實澱粉能成功地被固定在矽膠基材中，由分析結果可知當矽膠與澱粉的摻混比為一時摻混效果最佳。由氣相吸附測試結果發現固定化澱粉對水與乙醇的吸附選擇比(Water/Ehanol uptake)是傳統吸附材分子篩3A的2.4倍。此外，經過固定化後的澱粉再生後吸附能力比未經處理澱粉高出約36.3%。實驗數據經等溫吸附方程式迴歸後，比較迴歸常數發現 Langmuir model為大部分吸附材吸附行為的最佳描述。基於上述結果固定化澱粉表現出更好的吸附選擇比和再生能力。因此，本研究製備的固定化澱粉可能在填充塔酒精脫水系統中具有更好的應用價值。

Ethanol gasoline is a mixture of anhydrous ethanol and diesel, which may replace gasoline contain lead, and serve as bio-fuel. If the water content of ethanol is less than 0.5 wt %, and it may be blended into gasoline used in engine. Otherwise, the engine should be redesigned. Zeolite 3A is a widely used adsorbent in industry for ethanol dehydration. However, it has a low efficiency with adsorption selectivity and regeneration. Recently, some investigators have tried to use biomass based materials as a replacement to Zeolite 3A, such as starch. However, starch powder was recovered after adsorption with water vapor, and significant decrease of its adsorption ability was observed. In the present study, starch was immobilized into silica gel using sol-gel method for solving these problems. Results of energy-dispersive x-ray analysis showed that the starch particles are successfully immobilized into silica gel. The selectivity of the new material was found to be 2.4 times than that of Zeolite 3A. The adsorption ability of the new material increased by about 36.3% compared to that of raw starch. Furthermore, data using isotherm models and R-square values analysis suggested that Langmuir model is the most suitable model for this adsorbent material. Based on the above results, the immobilized starch was proven to be superior in terms of adsorption selectivity and regeneration ability over other adsorbents. Thus, this adsorbent material might be a potential adsorbent for application in ethanol dehydration systems.

摘要 I
Abstract II
致謝 II
總目錄 IV
圖目錄 VIII
表目錄 X
第一章 緒論 1
1-1 研究動機 1
1-2 研究目的及內容 2
第二章 文獻回顧與理論背景 4
2-1 醇水分離程序 4
2-1-1 共沸蒸餾脫水 4
2-1-2 滲透蒸發脫水 7
2-1-3 分子篩吸附脫水 8
2-2 生物吸附材 9
2-2-1 澱粉的結構 11
2-2-2 澱粉的物理特性 13
2-2-3 澱粉的糊化 16
2-3 固定化 18
2-3-1 矽膠固定化 20
2-4 矽膠 21
2-4-1 溶膠-凝膠過程 25
2-4-2 多孔矽膠形成過程 26
2-5 吸附現象 29
2-5-1 等溫吸附曲線 30
2-5-2 Langmuir等溫吸附方程式 34
2-5-3 BET等溫吸附方程式 34
2-5-4 其他等溫吸附方程式 35
第三章 實驗系統 41
3-1 實驗內容 41
3-2 實驗藥品 43
3-3 實驗儀器 44
3-4 混合材料製備方法 45
3-5 氣相吸附實驗方法 49
第四章 結果與討論 51
4-1 澱粉矽膠和M2B矽膠材料分析 51
4-1-1 澱粉矽膠的材料分析 51
4-1-2 M2B矽膠材料分析 55
4-2 吸附的前處理條件 58
4-3 吸附系統可信度驗證 60
4-4 吸附材吸附性能測試 62
4-5 不同顆粒大小對重複吸附的影響 67
4-6 混合材料老化測試 71
4-6-1 SS-3吸附水老化測試 71
4-6-2 SS-4吸附水老化測試 73
4-6-3 SS-4 吸附乙醇老化測試 76
4-7 吸水材M2B性能測試 79
4-7-1 M2B的吸附測試 79
4-7-2 M2B與矽膠混合後的吸附測試 82
4-7-3 M2B與矽膠混合後的老化測試 83
4-8 等溫吸附式的迴歸與探討 85
4-8-1 吸附材的迴歸結果討論 86
4-8-2 吸水材的迴歸結果討論 88
第五章 結論 92
5-1 結果討論 92
5-2 未來研究方向 94
參考文獻 95
Appendix I. 99
Appendix II. 101

Figure 2 - 1 Azeotropic distillation process 6
Figure 2 - 2 Extractive distillation process 6
Figure 2 - 3 Mechanism of pervaporation 7
Figure 2 - 4 Apparatus of Adsorptive distillation 8
Figure 2 - 5 The development of bio-absorption materials 11
Figure 2 - 6 α-1, 4 glycosidic bonds with the glucose residues linked 13
Figure 2 - 7 α-1, 6 glycosidic bonds with the glucose residues linked 13
Figure 2 - 8 Starch swelling condition (microscope) in different temperature 15
Figure 2 - 9 Starch solution gelatinization (swelling) characteristics 18
Figure 2 - 10 Irreversible enzyme immobilization method 19
Figure 2 - 11 Reversible enzyme immobilization method 19
Figure 2 - 12 The mechanisms of starch immobilized with silica gel 21
Figure 2 - 13 Development of sol - gel process 24
Figure 2 - 14 Schematic representation of gel surface at the beginning of stage 27
Figure 2 - 15 Plot of rate of water loss against water in the gel for various initial thickness gel section 28
Figure 2 - 16 IUPAC classification of isotherm 31
Figure 3 - 1 Experiment process 42
Figure 3 - 2 Preparation of hybrid silica gel procedure 46
Figure 3 - 3 Preparation of M2B hybrid silica gel procedure 48
Figure 3 - 4 Adsorption equipment 50
Figure 4 - 1 Starch Immobilized on silica gel inner surface 53
Figure 4 - 2 Different ratio of starch in silica gel 53
Figure 4 - 3 EDX mapping for SS-5 hybrid material 54
Figure 4 - 4 The molecular packing diagram of 1 (blue circles stand for oxygen atoms of lattice water, hydrogen atoms were omitted for clarity) 56
Figure 4 - 5 Different magnifications of M2B hybrid material 57
Figure 4 - 6 Adsorption isotherms of the regenerated starch at different degas temperatures 59
Figure 4 - 7 Water, methanol and ethanol adsorption isotherms for potato starch(h=P/P0) 61
Figure 4 - 8 Water adsorption isotherms for potato starch (experiment data) 62
Figure 4 - 9 Isotherms of water adsorption at 25oC 64
Figure 4 - 10 Isotherms of ethanol adsorption at 25oC 65
Figure 4 - 11 Comparison of the adsorption ratio of water to ethanol at 25oC 66
Figure 4 - 12 Adsorption time vs. percentage of water adsorption capacity at 25oC 66
Figure 4 - 13 Adsorption isotherms of original starch reused test 69
Figure 4 - 14 Adsorption isotherms of small size starch reused test 70
Figure 4 - 15 Isotherms of SS-3 water adsorption in reused test at 25oC 72
Figure 4 - 16 Isotherms of SS-4 water adsorption in reused test at 25oC 74
Figure 4 - 17 SS-3 reused time vs. water uptake in P/P0=0.6 75
Figure 4 - 18 SS-4 reused time vs. water uptake in P/P0=0.6 75
Figure 4 - 19 Isotherms of SS-4 ethanol adsorption in reused test at 25oC 77
Figure 4 - 20 SS-4 reused time vs. ethanol uptake in P/P0=0.6 78
Figure 4 - 21 Ratio of SS-4 adsorb water to ethanol 78
Figure 4 - 22 M2B water uptake compared with other absorption materials at 25oC 80
Figure 4 - 23 M2B and M2B silica ethanol uptake compared with other absorption materials at 25oC 80
Figure 4 - 24 Relative of water uptake vs. time(hr) at 25oC 81
Figure 4 - 25 Regeneration test of M2B hybrid with silica gel 84
Figure 4 - 26 M2B with silica reused times vs. water uptake in P/P0=0.6 84

Table 1 - 1 Ratio of water adsorptive capacity to ethanol adsorptive capacity at relative pressure at 0.6 3
Table 2 - 1 Different distillation methods used by the entrainer 5
Table 2 - 2 Composition of Starch 12
Table 2 - 3 Comparison of adsorption mechanism 30
Table 3 - 1 Experimental chemicals 43
Table 3 - 2 Experimental Experiments 44
Table 3 - 3 The proportion of starch and TEOS mixture 46
Table 4 - 1 EDX Element analysis of hybrid material 54
Table 4 - 2 Surface properties of the sorbents 54
Table 4 - 3 Element analysis of M2B hybrid material 56
Table 4 - 4 Ratio of adsorption water to ethanol in gas phase at P/P0=0.6 65
Table 4 - 5 Nanoparticles of potato starch and cassava starch 68
Table 4 - 6 Original starch adsorption reduce percent versus reuse times at P/P0=0.6 69
Table 4 - 7 Small size starch adsorption reduce percent versus reuse times at P/P0=0.6 70
Table 4 - 8 Percentage of the reduction of SS-3 water adsorption versus reused times at P/P0=0.6 72
Table 4 - 9 Percentage of the reduction of SS-4 water adsorption versus reused times at P/P0=0.6 74
Table 4 - 10 Percentage of the reduction of SS-4 ethanol adsorption versus reused times at P/P0=0.6 77
Table 4 - 11 Ratio of adsorption water to ethanol in gas phase at P/P0=0.6 82
Table 4 - 12 Water adsorption using Langmuir model and BET model of the regression results at 25oC 89
Table 4 - 13 Ethanol adsorption using Langmuir model and BET model of the regression results at 25oC 90
Table 4 - 14 Zeolite 3A using different isotherm models regression results at 25oC (ethanol adsorption) 91

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