臺灣博碩士論文加值系統

本論文係有關微/奈米鐵粉水熱產氫之研究，探討反應溫度、鐵粉含量、鐵粉粒徑以及觸媒添加量對產氫速率之影響。首先利用市售鐵粉與水反應，發現所產出之氣體冷凝後經氣相層析儀證實為高純度氫氣，且其產氫速率隨反應溫度與鐵粉含量增加而上升，隨鐵粉粒徑增大而下降。又奈米鐵粉產氫速率遠大於微米鐵粉，微米鐵粉在反應溫度低於100℃幾乎觀察不到氫氣的生成，而奈米鐵粉在反應溫度90℃依舊有大量氫氣產生，但奈米鐵粉反應長時間易有燒結現象發生，使反應不完全。其次使用置換反應在微米鐵粉上沉積鈀觸媒，三種不同粒徑之微米鐵粉隨著鈀觸媒沉積量的增加，產氫速率隨之增加，沉積鈀觸媒後45μm鐵粉其產氫效果優於3μm鐵粉，推測係因45μm鐵粉為扁平狀，且其表面有許多深淺不一的裂痕，有助於鐵粉表面積的增加與鈀觸媒的沉積，進而提升與水反應產氫的效能所致。沉積鈀觸媒後的45μm鐵粉，其產氫轉化率可從12.6%提升至98.7%，且三種不同粒徑之微米級鐵粉沉積鈀觸媒後其轉化率均可達80%以上，顯示鈀具有非常良好的催化效果，適用於沉積在各種粒徑及形態之鐵粉上。本研究所發展之鐵粉水熱產氫製程具有成本低廉、產出之氫氣純度極高、製程簡單易於大量生產的優點，極具實用化潛力。

This thesis concerns the hydrothermal generation of hydrogen gas by micron- and nano-iron powders. Investigate the hydrogen generation rate affected by reaction temperature, iron amount, iron particle size and the amount of catalyst added. First, this research used commercially iron reacted with water, finding that the gas of experiment produced after condensation was confirmed to high purity hydrogen by GC, and the hydrogen generation rate increased with increasing reaction temperature and iron amount, decreasing with increasing the particle size of iron. And the hydrogen generation rate of nano-iron much faster than micron-iron.There could not observe hydrogen generation by micron-iron when reaction temperature lower than 100℃, but there were still produced numerous of hydrogen by nano-iron when reaction temperature at 90℃.The nano-iron tended to be sintered if reaction for long time. It will cause the reaction incomplete. Secondly, using replacement reaction deposited the palladium catalyst on the micron-iron. Three different sizes of micron-iron of the hydrogen generation rate increased with increasing the amount of palladium deposited. The hydrogen generation rate of 45μm iron was better than 3μm iron after deposited the palladium on the iron surface, presumably due to there had many varying depth of cracks on 45μm iron surface and the shape of 45μm iron similar to flat, this structure contributed to increase the surface area of iron and deposit the palladium catalyst, then promoted the efficacy of hydrogen generation from iron with water. The conversion of 45μm iron was from 12.6% promoted to 98.7% after deposited the palladium on the iron surface. The conversion of three different sizes of micron-iron could reach above 80% after deposited the palladium on the iron surface. Show the palladium had very good catalytic activity, could deposit on iron for any size and shape.
This study developed the process of hydrothermal generation of hydrogen gas by iron powders had the advantage include: low cost, the hydrogen of generation had high purity, process simple and easy to mass production, exist the potential of practical.

總目錄
中文摘要 I
英文摘要 II
誌謝 IV
總目錄 V
表目錄 VII
圖目錄 VIII
符號 XI


第一章 緒論 1
1.1 奈米材料與奈米科技 1
1.1.1 前言 1
1.1.2 奈米材料的特性與應用 3
1.2 氫能 6
1.2.1 氫能簡介 6
1.2.2 產氫方法 8
1.2.3 氫的儲存 23
1.2.4 氫的應用 25
1.3 研究動機與內容 28
第二章 基礎理論 29
2.1 觸媒催化理論 29
2.1.1 觸媒簡介 29
2.1.2 觸媒之製備 31
2.1.3 催化反應之分類 35
第三章 實驗部分 39
3.1 藥品與儀器 39
3.1.1 藥品 39
3.1.2 儀器 40
3.1.3 材料 40
3.2 製備方式 41
3.2.1鐵粉前製處理 41
3.2.2 觸媒在鐵粉表面之沉積 41
3.3 特性分析 43
3.4 鐵粉水熱產氫之實驗方法 45
3.5 以表面沉積觸媒之鐵粉水熱產氫的方法 47
第四章 結果與討論 49
4.1 微/奈米鐵粉水熱法產氫 49
4.1.1 微/奈米鐵粉之基本物性 49
4.1.2 鐵粉水熱產氫 52
4.2 以表面沉積觸媒之鐵粉水熱產氫 59
4.2.1 沉積不同觸媒之鐵粉產氫速率比較 59
4.2.2 鈀/鐵之基本物性 61
4.2.3 鈀/鐵水熱產氫 70
4.2.3 氫氣鑑定 79
4.2.4 水熱產氫轉化率及氫氣生成莫耳數計算 80
4.2.5 文獻比較 84
第五章 結論 85
參考文獻 87
自述 98


表目錄
表1.1 奈米材料的特性所對應之應用範圍 5
表1.2 微、奈米鐵粉及雙金屬奈米鐵粉在室溫下產氫速率比較 16
表1.3 鐵粉(200 mesh)與水經由HS¯催化產氫轉化率比較 16
表1.4 常用的儲氫方法及其優缺點 24
表2.1 非均相觸媒之初步分類 30
表2.2 不同物質的氧化還原電位 33
表2.3 常見的置換反應 34
表4.1 沉積不同濃度鈀觸媒之3μm鐵粉EDS分析數據 66
表4.2 沉積不同濃度鈀觸媒之45μm鐵粉EDS分析數據 67
表4.3 沉積不同濃度鈀觸媒之60 mesh鐵粉EDS分析數據 68
表4.4 沉積不同濃度鈀觸媒之3μm鐵粉EDS分析數據與理論值比較 69
表4.5 沉積不同濃度鈀觸媒之45μm鐵粉EDS分析數據與理論值比較 69
表4.6 沉積不同濃度鈀觸媒之60mesh鐵粉EDS分析數據與理論值比較 69
表4.7 不同粒徑鐵粉沉積觸媒前後轉化率之比較 81
表4.8 利用XRD與AA計算之轉化率比較 82
表4.9 水熱反應後生成氫氣莫耳數比較 83
表4.10 相關文獻比較 84






圖目錄
圖1.1 奈米科技開發在不同領域之應用 2
圖1.2 粒子形態(0D-3D)與能量狀態之關係 4
圖1.3 粒子大小與原子在粒子內部及表面分佈比例之關係 4
圖1.4 氫是二次能源─氫與電的互換性 7
圖1.5 電解水製氫的過程示意圖 10
圖1.6 水熱分解時生成物與溫度的關係 10
圖1.7 Steam-Iron process氧化還原步驟流程圖 14
圖1.8 利用電化學方式還原氧化鐵之裝置圖 14
圖1.9 (a) 純鐵與水蒸氣反應產氫速率與反應溫度關係圖；(b) 鉬/鐵與水蒸氣反應產氫速率與反應溫度關係圖 15
圖1.10 生物質能在能量循環中的關係 20
圖1.11 生物質製氫方法 20
圖1.12 再生能源製氫與化石能源製氫之比較 21
圖1.13 燃料電池的動作原理與小型燃料電池 26
圖1.14 燃料電池與渦輪引擎的電能、熱能轉換效率 26
圖1.15 連接能源供給、產業間連動與社會體系的氫網路 27
圖2.1 反應中有無添加觸媒之活化能差別示意圖 30
圖2.2 非均相觸媒催化反應速率常數與反應溫度之關係示意圖 38
圖3.1 產氫裝置圖 46
圖4.1 不同粒徑鐵粉反應前SEM圖 50
圖4.2 100nm、3μm及45μm鐵粉反應前XRD分析圖譜 51
圖4.3 60mesh鐵粉反應前XRD分析圖譜 51
圖4.4 微米鐵粉(3μm)在不同鐵粉含量下產氫速率比較 53
圖4.5 不同反應溫度所產生的飽和蒸氣壓含量 54
圖4.6 微米鐵粉(3μm)在不同反應溫度下產氫速率比較 54
圖4.7 奈米鐵粉(100 nm)在不同反應溫度下產氫速率比較 55
圖4.8 奈米鐵粉(100 nm)在不同反應溫度下之XRD分析圖譜 55
圖4.9 不同粒徑鐵粉在相同反應條件下產氫速率比較 57
圖4.10 不同粒徑鐵粉水熱反應後之XRD分析圖譜 57
圖4.11 不同粒徑鐵粉水熱反應後SEM圖 58
圖4.12 沉積不同觸媒之微米鐵粉(3μm)產氫速率比較 60
圖4.13 鈀觸媒與鋅粒子反應之示意圖 60
圖4.14 沉積不同濃度鈀觸媒之3μm鐵粉反應前XRD分析圖譜 62
圖4.15 沉積不同濃度鈀觸媒之45μm鐵粉反應前XRD分析圖譜 62
圖4.16 沉積不同濃度鈀觸媒之60mesh鐵粉反應前XRD分析圖譜 63
圖4.17 SEM mapping分析圖 63
圖4.18 沉積2mM PdCl2之3μm鐵粉EDS分析圖譜 66
圖4.19 沉積鈀觸媒前後的3μm鐵粉反應前SEM圖 66
圖4.20 沉積2mM PdCl2之45μm鐵粉EDS分析圖譜 67
圖4.21 沉積鈀觸媒前後的45μm鐵粉反應前SEM圖 67
圖4.22 沉積2mM PdCl2之60 mesh鐵粉EDS分析圖譜 68
圖4.23 沉積鈀觸媒前後的60 mesh鐵粉反應前SEM圖 68
圖4.24 沉積不同濃度鈀觸媒的3μm鐵粉與單純3μm鐵粉水熱產氫速率 比較 71
圖4.25 沉積不同濃度鈀觸媒的3μm鐵粉反應後之XRD分析圖譜 71
圖4.26 沉積不同濃度鈀觸媒的3μm鐵粉產氫後SEM圖 72
圖4.27 沉積不同濃度鈀觸媒的45μm鐵粉與單純45μm鐵粉水熱產氫速率比較 74
圖4.28 沉積不同濃度鈀觸媒的45μm鐵粉反應後之XRD分析圖譜 74
圖4.29 沉積不同濃度鈀觸媒的45μm鐵粉產氫後SEM圖 75
圖4.30 沉積不同濃度鈀觸媒的60 mesh鐵粉與單純60 mesh鐵粉水熱產 氫速率比較 77
圖4.31 沉積不同濃度鈀觸媒的60 mesh鐵粉反應後之XRD分析圖譜 77
圖4.32 沉積不同濃度鈀觸媒的60 mesh鐵粉產氫後SEM圖 78
圖4.33 水熱反應產生之氣體經由氣相層析儀分析之結果 79

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