臺灣博碩士論文加值系統

本實驗利用傳統反應器以及膜反應器進行甲烷水蒸氣重組實驗。膜反應器係以內外套管構成，外管為不鏽鋼管，內管為多孔性不鏽鋼管，並以無電鍍法析鍍25μm之緻密鈀銀合金膜，作為分離氫氣之用，內外管間填充商業鎳觸媒進行反應；傳統反應器則是將作為內管之膜管以相同直徑的無孔洞不鏽鋼管取代。實驗結果在不同的實驗參數下（如溫度、壓力、WHSV以及水與甲烷的莫耳數比），詳細的探討甲烷轉化率以及氫氣移出率；此外，就甲烷轉化率方面，比較膜反應器以及傳統反應器。具有高氫產率、高甲烷轉化率，以及相對低的一氧化碳產率的最佳化條件出現在H2O/CH4之莫耳數比為2、溫度為470℃、壓力在7大氣壓以及WHSV在0.3的環境下。

In this study, steam reforming of methane was carried out in a traditional reactor or a membrane reactor. The membrane reactor was consisted of two coaxial tubes, of which the outer tube was a stainless steel tube and the inner one was a porous stainless steel tube, electrolessly plated, with palladium/silver alloy, being dense and important for separation and purification of hydrogen. To perform the reforming reaction, a commercial Ni/MgAl2O3 reforming catalyst was packed into the annular space. The traditional reactor was made by replacing the porous inner tube with a dense stainless steel tube of the same diameter. Methane conversion and hydrogen extraction ratio were studied in detail under different operating conditions with ranging parameters such as temperature, pressure, space velocity and steam-to-methane feed ratio. Moreover, experimental results in terms of methane conversion for the membrane reactor were compared with those obtained using a traditional reactor. For high hydrogen production, high methane conversion and relatively low carbon monoxide yield, the optimum conditions are: steam to methane ratio of 2 , temperature of 470℃, pressure at 7atm and space velocity of 0.3h-1.

誌謝 I
摘要 II
Abstract III
目錄 IV
圖目錄 VIII
表目錄 XI
壹、前言 1
貳、原理 4
2.1 薄膜反應器的應用 4
2.2 薄膜分類 4
2.3 無機薄膜 5
2.3.1 無機薄膜分離機制 5
2.3.2 無機薄膜構造 7
2.3.3 無機薄膜分離程序 8
2.4 鈀金屬特性 9
2.4.1 鈀合金膜氣體滲透行為 10
2.4.1-1 氣體於孔洞基材的傳送機制 10
2.4.1-2 氫氣於緻密鈀膜的傳送機制 12
2.4.2 鈀金屬的氫脆現象 14
2.4.3 氫氣在鈀及鈀銀合金膜的擴散與溶解 17
2.5 鈀合金薄膜製備方法 19
2.5.1 化學氣相沈積法(chemical vapor deposition，CVD) 20
2.5.2 濺鍍法(sputtering) 20
2.5.3 噴霧裂解法(spray pyrolysis) 21
2.5.4 電鍍法(electroplating) 23
2.5.5 無電鍍法(electroless plating) 24
2.6 影響鈀合金膜活性之因素 29
2.7 膜反應器的類型 29
2.8 鈀銀合金膜管之滲透分析 31
2.9 降低氫氣逆滲透(back-permeation)之方法 32
參、實驗方法 34
3.1 實驗藥品、管材及氣體 34
3.2 儀器 36
3.2.1 分析儀器 36
3.2.2 其他儀器 36
3.3 實驗步驟： 38
3.3.1 鈀銀合金膜管之滲透分析(H2/N2) 38
3.3.2 甲烷水蒸氣重組反應 42
3.3.2-1 鈀銀合金膜反應器進行甲烷水蒸氣重組實驗 42
3.3.2-2 傳統反應器進行甲烷水蒸氣重組實驗 44
3.3.2-3 鈀銀合金膜反應之空白實驗 44
3.3.3 甲烷水蒸氣重組反應產物分析 44
肆、結果與討論 47
4.1 氫氣滲透行為 47
4.1.1 氫氣在鈀膜中的透過行為 47
4.1.2 選擇率及活化能 48
4.2 利用鈀銀合金膜反應器進行甲烷水蒸氣重組實驗 51
4.2.1 操作參數對甲烷轉化率的影響 51
4.2.1-1 操作溫度的影響： 51
4.2.1-2 反應壓力的影響 54
4.2.1-3 WHSV(weight hourly space velocity) 的影響 57
4.2.1-4 水與甲烷莫耳比 (nH2O/nCH4) 的影響 59
4.2.1-5 操作參數與甲烷轉化率之比較 60
4.2.2 氫氣移出率 62
4.2.3 CO產率的比較 66
4.3 積碳的形成 67
伍、結論 74
陸、建議 76
柒、附錄 77
7.1 甲烷水蒸氣重組可能出現的反應方程式 77
7.2 實驗數據定義 78
7.3 計算理論平衡轉化率 79
捌、參考文獻 84

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