臺灣博碩士論文加值系統

當燃料電池技術備受重視時，氫氣的生產在過去的幾十年裡為重要的，研究的趨勢是以改善現有的技術和開發新的程序，以提高氫氣產率及生成高純度氫氣。
本研究是以無電鍍法析鍍鈀和銀在多孔性不鏽鋼管上，製備緻密性鈀銀合金膜，並將鈀銀合金膜反應器置於反應系統中，填充自行製備之(Ni/CeO2/Al2O3)觸媒，進行水煤氣轉化反應產生高純度氫氣，在不同的操作溫度( 350-425 oC)和壓力( 1.5-7 atm)下，膜反應器優于傳統填充床反應器。
經由實驗結果顯示鈀合金膜反應器進行水煤氣轉化反應，能有效提高氫氣產率得到高純度氫氣，改善CO轉化率高于平衡CO轉化率，在溫度為425℃、壓力為5 atm及H2O/CO進料比為3時，有最佳之CO轉化率99.73% ，氫氣產率為96.37%，最大氫氣滲透通量15.08 mol/m2•h。

Hydrogen production has become an important issue over the past decades, but nowadays it is of greater interest because of the rapid progress of the fuel-cell technology . This situation has intensified the research tending both to improve the existing technologies and to develop new processes to generate and purify H2.
A dense Pd-Ag alloy membrane prepared by electroless plating of Pd and Ag on porous stainless steel tube was used as the reactor, in which the Ni/CeO2/Al2O3 catalyst was packed for producing high purity hydrogen via the water gas shift reaction. The reaction was performed under different operating temperatures (350 - 425 oC) and pressures (1.5 - 7 atm) to conclude the advantage of the membrane reactor when compared to the traditional packed – bed reactor.
The experimental results show that in the palladium alloy membrane reactor conducting the water gas shift reaction, high-purity hydrogen yield can be effectively enhanced and the CO conversion can exceed the equilibrium value. When the reaction temperature is 425 �窢, pressure of 5 atm and H2O/CO ratio of 3, we can get the best conversion rate of 99.73 %, hydrogen production rate of 96.37% and hydrogen permeation amount of 15.08 mol/m2 h.

誌謝 I
摘要 II
Abstract III
目錄 IV
圖目錄 VIII
表目錄 XI
第一章 緒論 1
1-1 前言 1
1-2 研究目的 4
第二章 原理及文獻回顧 5
2-1 無機薄膜 5
2-1-1 無機薄膜機制 5
2-1-2 無機薄膜分離程序 6
2-2 鈀金屬特性 7
2-2-1 鈀合金膜載體 7
2-2-2 鈀合金膜製備方法 8
2-2-3 鈀膜中氫氣的擴散機制 12
2-3 無機薄膜反應器 17
2-4 鈀膜反應器的應用 19
2-5 雜質對鈀膜中氫氣滲透行為的影響 22
2-5-1 惰性氣體共存引起氫分壓下降 24
2-5-2 非氫組分在鈀膜表面的競爭吸附 25
2-5-3 積碳的影響 27
2-5-4 硫的影響 28
2-6 觸媒的應用 28
第三章 實驗方法 30
3-1 實驗藥品和儀器 30
3-1-1 實驗藥品 30
3-1-2 實驗氣體 31
3-1-3 實驗管材 31
3-1-4 實驗儀器 32
3-2 實驗流程 33
3-2-1 鈀合金膜製備程序[49] 33
3-2-2 鈀銀合金膜管滲透分析 34
3-2-3 觸媒的製備 36
3-2-4 水煤氣轉化反應(Water gas shift reaction) 38
3-2-5 水煤氣轉化反應產物分析 40
3-3 特性分析 42
第四章 結果與討論 44
4-1 鈀銀膜氣體滲透行為 44
4-1-1 鈀銀膜滲透測試 44
4-1-2 氫氣滲透行為 44
4-1-3 H2/N2滲透選擇率和活化能 45
4-2 觸媒之性質 48
4-2-1 觸媒之熱重分析 48
4-2-2 觸媒表面性質 50
4-2-3 觸媒晶相分析 50
4-2-4 觸媒之比表面積分析 55
4-3 水煤氣轉化反應 56
4-3-1 水煤氣轉化平衡反應式 56
4-3-2 不同條件參數之水煤氣轉化反應 57
4-3-2-1 反應壓力之影響 58
4-3-2-2 H2O/CO進料比之影響 60
4-3-2-3 操作溫度之影響 62
4-3-3 氫氣產率 64
4-3-4 氫氣移出率 64
第五章 結論 67
第六章 附錄 68
6-1 水煤氣轉化反應分析 68
第七章 參考文獻 74

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