中文摘要
氫氣在未來的能源發展裡，佔著一席重要的地位，因此許多學者皆著重在利用不同的脫氫反應進行產氫的研究。而在本論文中，將討論利用鈀膜反應器進行乙醇脫氫的研究，藉由鈀膜吸氫的功能，反應產生的氫氣可直接從反應相經由鈀膜滲透，造成反應相中氫氣分壓降低，不僅可以增加轉化率，更可以從反應器的滲透端直接得到高純度的氫氣（3-7N）。實驗之鈀膜管是以無電鍍技術所製成的，將之操作在溫度範圍為350℃-450℃、壓力範圍為1-10atm的反應環境中進行鈀膜透氫行為與乙醇脫氫反應的研究，使用之觸媒主要為MDC-3銅鋅觸媒，利用改變實驗的操作參數來研究鈀膜反應器內進行乙醇脫氫反應最佳之操作條件，進而與其他反應器模式比較。經由實驗結果發現當450℃、10atm、進料流速為9cc/h、WHSV=5的時候有最大的氫氣滲透量（0.0281mole/h），且鈀膜氫氣回收率為76.9﹪。而在相同進料流速（9cc/h）與觸媒量（1.4688g）下，350℃、10atm時緻密型鈀膜的乙醛產率（20.19﹪）為多孔型鈀膜乙醛產率（11.25﹪）的1.8倍，更是傳統反應器乙醛產率（6.95﹪）的2.9倍，而且乙醇轉化率（34.43﹪）會高於乙醇的平衡轉化率（21.91﹪）。然而實驗後所得的結果與實驗前預期並模擬出乙醇轉化率可以達到趨近於100﹪的結果相差甚遠，因此在綜合實驗過程中的經驗後而討論出幾項導致結果低於預期的因素：1.進行反應時並沒有將sweep gas考慮入反應器中。2.MDC-3銅鋅觸媒對乙醇的脫氫反應的活性與選擇性並不是很高。3.由於乙醇脫氫與乙醇脫水的競爭反應，且反應器中之反應物並沒有和觸媒床做充分的接觸，而產物中之氫氣也沒有和鈀膜表面做充分的接觸。因此造成乙醛產率偏低、乙醛選擇率皆偏低。

Abstract
The dehydrogenation of saturated hydrocarbons to alkenes used as an intermediate in the production of new fuels and fuel additives, and hydrogen has become more and more popular in the past several decades. In this paper, we investigated the ethanol dehydrogenation to produce acetaldehyde and hydrogen in a palladium membrane reactor. With the separation of hydrogen by permeation through a palladium membrane, the thermodynamic equilibrium was allowed to displace to a new condition. It cannot only shift the equilibrium to increase the conversion, but also obtain the high purity of hydrogen from the permeation side. The reactor used a porous stainless steel tube that was electrolessly plated palladium with a thickness c.a. 15μm, was industrial catalyst loaded MDC-3 for the dehydrogenation test. With the change between the operation parameters, we can find the optimum operation condition in a palladium membrane reactor, and compare with conventional reactor. According to the experimental data, the maximum production of pure hydrogen obtained was 0.0281mole/h and the maximum palladium membrane recovery yield of hydrogen form ethanol was found to be 76.9﹪. For the dehydrogenation of ethanol to acetaldehyde in a dense membrane reactor, the largest enhancement in ethanol conversion was a factor of 1.49 greater than a porous membrane reactor, 1.57 greater than equilibrium conversion and 1.95 greater than a conventional reactor. But it still had a large difference between the experiment and the simulation data. The experimental result was much lower than simulation that was attributed: 1.the effect of sweep is ignored. 2.The low activity and low acetaldehyde selectivity catalyst. 3. Existence of by passing and challenge effect that caused inadequate contact between the reactant, catalyst bed and the membrane surface.

目錄
中文摘要．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．I
Abstract．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．III
目錄．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．． ．V
圖目錄．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．VIII
表目錄．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．XI
壹、前言．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．1
貳、原理．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．4
2.1無機薄膜反應器介紹．．．．．．．．．．．．．．．．．．．．．4
2.1.1薄膜（membrane）介紹．．．．．．．．．．．．．．．．．．4
2.1.2無機穿透膜的種類．．．．．．．．．．．．．．．．．．．．．5
2.1.2.1多孔型薄膜．．．．．．．．．．．．．．．．．．．．．．．．5
2.1.2.2緻密型薄膜．．．．．．．．．．．．．．．．．．．．．．．．7
2.1.3無機薄膜反應器種類與應用．．．．．．．．．．．．．．．7
2.2鈀過渡元素的基本特性．．．．．．．．．．．．．．．．．．．10
2.2.1歷史背景．．．．．．．．．．．．．．．．．．．．．．．．．．．10
2.2.2鈀金屬的氫脆現象．．．．．．．．．．．．．．．．．．．．．11
2.2.3鈀合金穿透膜．．．．．．．．．．．．．．．．．．．．．．．．11
2.2.4氫原子的傳送機構．．．．．．．．．．．．．．．．．．．．．12
2.3鈀及其合金穿透膜製備方法．．．．．．．．．．．．．．．．15
2.4乙醇脫氫反應．．．．．．．．．．．．．．．．．．．．．．．．．．19
2.4.1鈀膜反應器進行脫氫反應之研究．．．．．．．．．．．19
2.4.2乙醇脫氫反應之反應機構．．．．．．．．．．．．．．．．20
參、實驗方法與步驟．．．．．．．．．．．．．．．．．．．．．．．．22
3.1藥品．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．34
3.2儀器裝置．．．．．．．．．．．．．．．．．．．．．．．．．．．．．36
3.3鈀膜的透氫行為．．．．．．．．．．．．．．．．．．．．．．．．39
3.4以鈀膜反應器進行乙醇脫氫反應研究．．．．．．．．．41
3.4.1乙醇脫氫反應反應物及產物定性、定量分析．．．42
3.4.2利用傳統反應器進行乙醇脫氫反應．．．．．．．．．．43
3.4.3利用多孔型鈀膜反應器進行乙醇脫氫反應．．．．． 44
3.4.4利用緻密型鈀膜反應器進行乙醇脫氫反應．．．．．45
3.4.4.1空白實驗（blank test）．．．．．．．．．．．．．．．．45
3.4.4.2薄膜實驗．．．．．．．．．．．．．．．．．．．．．．．．45
肆、結果與討論．．．．．．．．．．．．．．．．．．．．．．．．．．．．54
4.1鈀膜透氫行為．．．．．．．．．．．．．．．．．．．．．．．．．．54
4.1.1多孔型鈀膜測試．．．．．．．．．．．．．．．．．．．．．．54
4.1.2緻密型鈀膜測試．．．．．．．．．．．．．．．．．．．．．．55
4.2傳統反應器進行乙醇脫氫反應．．．．．．．．．．．．．．56
4.3利用鈀膜反應器進行乙醇脫氫反應．．．．．．．．．．．57
4.3.1空白實驗．．．．．．．．．．．．．．．．．．．．．．．．．．．57
4.3.2多孔型鈀膜．．．．．．．．．．．．．．．．．．．．．．．．．．58
4.3.3緻密型鈀膜．．．．．．．．．．．．．．．．．．．．．．．．．．59
4.3反應器模式對乙醇脫氫的影響．．．．．．．．．．．．．．61
伍、結論．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．102
陸、附錄．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．105
柒、參考文獻．．．．．．．．．．．．．．．．．．．．．．．．．．．．．110

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