臺灣博碩士論文加值系統

隨著環保意識的崛起，任何會污染大自然生態的發展應用都將受到限制。為因應這股綠色潮流，研究發展新能源的產生，變成大家所重視的課題。在新能源中，以氫能源的開發最受注目。本研究的目的是探討利用鈀銀合金膜反應器進行乙醇自熱化水蒸氣重組反應生產氫氣，利用氫氣滲透的特性，在膜管的滲透端收集高純度的氫氣。本實驗所使用的鈀銀合金膜管是以無電鍍法自製而成，其膜厚約為30 μm，操作溫度範圍在320℃ ~ 450℃，壓力控制在3 ~ 9 atm，以商用觸媒MDC-3進行乙醇自熱化水蒸氣重組反應。反應物水和乙醇之莫耳比為1：1 (nH2O/nC2H5OH = 1 )；而氧氣和乙醇之莫耳比範圍為0到0.7 (nO2/nC2H5OH = 0 ~ 0.7)；進料流速範圍為0.39 ~ 0.63 mL/min ( WHSV= 5 ~ 8 h-1)。由實驗結果發現，加入氧氣的多寡，會決定總反應的熱平衡。當nO2/nC2H5OH = 0時，即是單純的水蒸氣重組反應，為吸熱反應，故在該反應條件下，在高溫低壓時(450℃、3 atm)有最大的乙醇轉化率82.07%。當nO2/nC2H5OH = 0.7時，則完全由氧化反應主導，為放熱反應。當nO2/nC2H5OH = 0.2時，總反應仍傾向於吸熱反應，高溫時，其反應結果接近於沒通氧時的結果，而低溫時(320℃)則可將轉化率提高至62%左右。在nO2/nC2H5OH = 0.2，WHSV= 8 h-1，9 atm，450℃時，因進料流量大且轉化率頗高，故有最大的氫氣滲透通量122.89 mole/m2*h.。

Along with environmental consciousness rising, any developments and applications which may be able to pollute the ecology will be restricted. In accordance to this green trend, searching for new energies and their development have become an important issue. Among all of the new types of energy, the evolution of hydrogen energy receives the most attention.
The goal of this study is to focus on hydrogen production by autothermal steam reforming of ethanol in a palladium-silver alloy membrane reactor. Hydrogen which only permeates through a palladium-silver alloy membrane can be collected on the permeation side with high purity. The palladium-silver alloy membrane tube used for this experiment was made by eletroless plating technique, with an overall thickness of about 30μm. An industrial catalyst MDC-3 was employed for autothermal steam reforming of ethanol reaction. The operating temperatures ranged from
320℃ to 450℃ and the pressures between 3atm to 9atm. The reactant of water/ethanol molar ratio is 1:1, the O2/ethanol molar ratio ranging between 0 to 0.7, and varying feed rate between 0.39 to 0.63 mL/min ( WHSV= 5 ~ 8 h-1). The experimental results show that the amount oxygen feed to the reactor will determine the thermal equilibrium of total reaction. It is a steam reforming reaction at nO2/nC2H5OH = 0, which is an endothermic reaction, so there is an optimal ethanol conversion of 82.07% at the lowest pressure and highest temperature (P= 3 atm, T= 450℃). When nO2/nC2H5OH = 0.7, the total reaction is dominated by the partial oxidation of ethanol, which is exothermic. At nO2/nC2H5OH = 0.2, the total reaction tends to be an endothermic reaction, but it behaves like a steam reforming reaction at high temperatures while at the low temperature (T= 320℃) the ethanol conversion is still promoted to 62% due to the presence of oxygen. At nO2/nC2H5OH = 0.2, WHSV= 8 h-1, 9 atm, and 450℃, the maximum fluxes of hydrogen of 122.89 mole/m2*h is obtained due to high feed rate and high ethanol conversion.

誌謝 I
中文摘要 II
ABSTRACT III
目錄 V
表目錄 VIII
圖目錄 IX
壹、前言 1
貳、原理 3
2.1氫的利用 3
2.2應用薄膜反應器產氫 3
2.3無機分離薄膜 4
2.3.1無機膜的分類 7
2.3.1.1無機膜的分離機制 7
2.3.1.2無機膜的應用型態 9
2.3.2多孔型薄膜 11
2.3.3緻密型薄膜 13
2.4無機膜反應器種類 14
2.4.1.產物移出型膜反應器 14
2.4.2.控制進料型膜反應器 14
2.4.3.催化活性型膜反應器 16
2.4.4無機膜反應器中薄膜特性要求 17
2.5鈀金屬的特性說明 18
2.5.1鈀金屬的發展由來 18
2.5.2鈀金屬之氫脆現象 18
2.5.3鈀合金穿透膜 20
2.5.4氫氣在鈀合金膜之傳送機制 26
2.6 鈀合金薄膜製備方法 31
2.6.1.化學氣相沈積法(chemical vapor deposition, CVD)【35-36】 31
2.6.2.物理氣相沈積 (physical vapor deposition, PVD) 【36】 31
2.6.3.濺鍍法(sputtering) 【37-38】 32
2.6.4.溶膠凝膠法(Sol-Gel) 【39-40】 34
2.6.5.無電鍍法(electroless plating) 【25, 28, 41-47】 34
2.7乙醇自熱化蒸氣重組反應 39
參、實驗方法與步驟 41
3.1 鈀銀合金膜管之氫氣/氮氣滲透選擇率 41
3.2乙醇自熱化蒸氣重組反應 42
3.2.1乙醇自熱化蒸氣重組反應產物之特性分析 42
3.3乙醇自熱化蒸氣重組反應的實驗步驟 48
3.3.1空白實驗（blank test） 49
3.3.2利用傳統反應器進行乙醇自熱化水蒸氣重組反應 50
3.4藥品 50
3.4.1氣相產物氣體 50
3.4.2液相產物藥品 50
3.4.3實驗用觸媒 51
3.4.4其他 51
3.5儀器裝置 51
肆、結果與討論 55
4.1鈀銀合金膜管滲透通量 55
4.2利用鈀銀膜反應器進行乙醇自熱化水蒸氣重組反應 56
4.2.1 空白實驗 56
4.2.2 不同通氧比率對乙醇轉化率的影響 56
4.2.3 不同通氧比率對CO和CO2選擇率的影響 58
4.2.4 不同WHSV比率對乙醇轉化率的影響 59
4.2.5 不同WHSV比率對CO及CO2選擇率的影響 59
4.3氫氣滲透通量 61
4.3.1氫氣滲透通量普遍之趨勢及現象 61
4.3.2 不同通氧比例之反應對氫氣滲透通量的影響 62
4.3.3 不同WHSV對氫氣滲透通量的影響 62
4.4傳統反應器進行反應 62
4.4.1 傳統反應器進行乙醇自熱化水蒸氣重組反應 63
4.4.2 傳統與鈀銀膜反應器比較乙醇自熱化水蒸氣重組反應結果 63
4.4.3 壓力與溫度對於鈀銀膜反應器提高乙醇轉化率的影響 63
伍、結論 94
陸、附錄 96
6.1乙醇自熱化水蒸氣重組可能出現的反應機構 96
6.2實驗數據的定義 96
柒、參考文獻 98

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