臺灣博碩士論文加值系統

本研究成功地建立固態硼氫化鈉錠水解產氫系統，並求得Ru/Al2O3觸媒之動力學參數。為了使產氫系統之儲氫量提高，先建立系統數學模式並分析影響系統之變數。系統中，利用蠕動式幫浦將進料水注入固態硼氫化鈉錠中，並且利用多孔不鏽鋼膜片當作水的分散器。固態硼氫化鈉錠為硼氫化鈉與觸媒粉末壓製而成，直徑為1.5 cm厚度為0.2 cm。系統的設計變數與操作變數為：硼氫化鈉與觸媒比例、燃料錠的孔隙度、操作溫度與進料水量等四者。由靈敏度分析結果得知，影響系統儲氫量最重要的二個變數是進料水量與操作溫度。這些變數會影響水的利用率。本研究針對系統進料水量在反應消耗、硼酸鈉結晶(NaBO2‧(xH2O))消耗及蒸發水三個部分分別進行討論。研究結果顯示，最佳操作條件為50℃，進料水量為0.0026 mL/min，能得到最高儲氫量為7 wt. %，實驗與模擬結果符合。

In this work, sodium borohydride hydrolysis systems for hydrogen generation were set-up and used to find the reaction kinetic model and kinetic parameters of Ru/Al2O3 catalyst. In order to efficiently enhance the hydrogen storage capacity of the solid sodium borohydride hydrolysis systems, a mathematical model was built and used to analyst and find out the dominant variables of the process. Water was injected by a rotary pump and dispersed via a porous stainless steel sheet into the surface of the NaBH4 tablet/Ru/Al2O3 with a 1.5 cm diameter and 0.2 cm thickness. The design and operating variables of the system are: The ratio of the weight of NaBH4 and Ru/Al2O3 catalyst, void fraction, operating temperature and water injection rate. From sensitivity analysis, the dominant variables of the hydrogen storage capacity of the system are: Water injection rate and operating temperature, these variables cause water utilization competition between water evaporation, reaction consumption and water crystallization (NaBO2‧(xH2O)). Finally, optimization of the hydrogen storage capacity for our system was done which resulted in a 7 wt. % hydrogen storage capacity maximum. The optimal operating temperature and water injection rate with a 0.25 W power generation were 50℃ and 0.0026 mL/min, respectively. The optimal simulation result was fitted with our experiment.

目錄
中文摘要 I
英文摘要 II
目錄 III
圖目錄 VII
表目錄 XI
第一章、緒論 1
1.1 背景 1
1.2 文獻回顧 4
1.3 研究動機 9
1.4 論文組織 9
第二章、實驗藥品與裝置介紹 11
2.1 實驗材料與設備 11
2.2 實驗裝置 13
2.2.1 硼氫化鈉水溶液產氫實驗裝置 13
2.2.2 固態硼氫化鈉錠產氫實驗裝置 16
2.3 實驗步驟 19
2.3.1、硼氫化鈉水溶液產氫實驗步驟 20
2.3.2 固態硼氫化鈉錠產氫實驗步驟 20
2.3.3 壓錠步驟 21
2.3.4 幫浦檢量線 23
2.3.5 多孔不鏽鋼片之孔洞量測 24
2.4 氫氣數據量測 25
2.5 數據處理 28
第三章、觸媒動力式分析 30
3.1 系統描述 30
3.2 操作溫度對硼氫化鈉水解產氫速率之影響 31
3.3 觸媒動力式 34
3.3.1 零階反應速率常數 35
3.3.2 一階反應速率常數之求解方式 39
3.3.3 L-H反應速率常數之求解方式 43
3.4 釕觸媒參數回歸 48
3.4.1 頻率因子與活化能回歸 48
3.4.2 L-H動力式之吸收常數 51
3.5 硼氫化鈉水溶液與固態硼氫化鈉錠之產氫實驗比較 52
3.6 結果與討論 55
第四章、固態硼氫化鈉錠水解產氫模式建立 56
4.1 系統描述 56
4.2 系統模式建立 58
4.2.1 模式假設 59
4.2.2 系統數學模式建立 60
4.2.3 水的利用率與硼酸鈉結晶個數 63
4.3 固態硼氫化鈉解產氫模擬結果與實驗驗證 65
4.3.1 基本個案分析 65
4.3.2 操作溫度對產氫曲線之影響 69
第五章、靈敏度分析與最適化系統儲氫量 72
5.1 實驗設計變數與操作變數 72
5.2 靈敏度分析 73
5.2.1孔隙度對水利用率之影響 74
5.2.2觸媒量對水利用率之影響 77
5.2.3進料水量對水利用率之影響 79
5.2.4操作溫度對水利用率之影響 82
5.3目標函數 84
5.4最適化系統儲氫量 86
5.5硼氫化鈉水解產氫之供氫量操作分析 89
5.6結果與討論 90
第六章、結論 91
符號說明 92
參考文獻 95

圖目錄
圖1-1、質子交換膜燃料電池產氫示意圖 2
圖2-1、硼氫化鈉水溶液水解產氫實驗與量測裝置圖 14
圖2-2、硼氫化鈉水溶液產氫實驗裝置示意圖 15
圖2-3、固態硼氫化鈉錠水解產氫實驗與量測裝置圖 17
圖2-4、固態硼氫化鈉錠水解產氫實驗與量測示意圖 18
圖2-5、瑪瑙研缽 22
圖2-6、壓錠模具 22
圖2-7、蠕動式幫浦減量線 23
圖2-8、多孔不鏽鋼膜片孔洞大小測定(Davg.=1μm) 25
圖2-9、溫度紀錄程式圖示 26
圖2-10、溫度紀錄程式操作介面 26
圖2-11、電子天秤紀錄程式圖 27
圖2-12、電子天秤紀錄程式操作介面 28
圖2-13、硼氫化鈉水解產氫(A)氫氣累積重量之數據平滑化(B)操作
溫度(C)氫氣流量 29
圖3-1、硼氫化鈉水溶液水解產氫反應器(A)示意圖，(B)實驗裝置
圖 30
圖3-2、(A)改變反應器操作溫度，氫氣流量對時間之關係圖
(B)操作溫度為40℃、50℃、60℃、70℃、80℃ 33
圖3-3、40℃之零階動力式模擬結果與實驗比較 37
圖3-4、50℃之零階動力式模擬結果與實驗比較 37
圖3-5、60℃之零階動力式模擬結果與實驗比較 38
圖3-6、70℃之零階動力式模擬結果與實驗比較 38
圖3-7、80℃之零階動力式模擬結果與實驗比較 39
圖3-8、40℃調整不同k所得誤差結果 40
圖3-9、40℃之一階動力式模擬結果與實驗比較 41
圖3-10、50℃之一階動力式模擬結果與實驗比較 41
圖3-11、60℃之一階動力式模擬結果與實驗比較 42
圖3-12、70℃之一階動力式模擬結果與實驗比較 42
圖3-13、80℃之一階動力式模擬結果與實驗比較 43
圖3-14、40℃調整不同k, Ka所得誤差結果 44
圖3-15、40℃之L-H動力式模擬結果與實驗比較 45
圖3-16、50℃之L-H動力式模擬結果與實驗比較 46
圖3-17、60℃之L-H動力式模擬結果與實驗比較 46
圖3-18、70℃之L-H動力式模擬結果與實驗比較 47
圖3-19、80℃之L-H動力式模擬結果與實驗比較 47
圖3-20、零階動力式利用線性回歸找到之頻率因子與活化能 49
圖3-21、一階動力式利用線性回歸找到之頻率因子與活化能 50
圖3-22、L-H動力式利用線性回歸找到之頻率因子與活化能 50
圖3-23、吸收常數利用線性回歸找到之焓跟熵 52
圖3-24、硼氫化鈉水溶液與固態硼氫化鈉錠產氫結果比較 54
圖3-25、固態硼氫化鈉錠崩解示意圖 54
圖4-1、固態硼氫化鈉錠產氫系統(A)示意圖，(B)實驗圖 57
圖4-2、反應區示意圖 58
圖4-3、結晶水個數與溫度關係 64
圖4-4、基本個案模擬與實驗結果圖 66
圖4-5、前段動態圖 68
圖4-6、反應區域變化示意圖 68
圖4-7、溫度變化之影響45℃ 70
圖4-8、溫度變化之影響50℃ 71
圖5-1、靈敏度分析取點方式 74
圖5-2、孔隙度對固態硼氫化鈉錠水解產氫系統各物流模擬結果 75
圖5-3、改變孔隙度對物流影響示意圖 76
圖5-4、相同反應區域觸媒量示意圖 76
圖5-5、觸媒量對固態硼氫化鈉錠水解產氫系統各物流模擬結果 77
圖5-6、改變觸媒量對物流影響示意圖 78
圖5-7、觸媒量小於0.0019 g之示意圖 79
圖5-8、進料水量對固態硼氫化鈉錠水解產氫系統，各物流模擬
結果 80
圖5-9、改變觸媒量對物流影響示意圖 81
圖5-10、改變觸媒量對物流影響示意圖 82
圖5-11、操作溫度對固態硼氫化鈉錠水解產氫系統，各物流模擬
結果 83
圖5-12、等產能曲線 85
圖5-13、最佳操作溫度條件 86
圖5-14、實驗驗證(FH2O=0.0026 mL/min、T=50℃) 88
圖5-15、產氫量需求變化時，最佳儲氫量之操作點 89

表目錄
表1-1、觸媒動力式文獻整理 7
表2-1、實驗藥品與材料 11
表2-2、實驗設備與儀器 12
表3-1、不同溫度之反應速率常數(零階) 39
表3-2、不同溫度之反應速率常數(一階) 43
表3-3、不同溫度之反應速率常數(L-H) 48
表3-4、不同動力式頻率因子與活化能結果 51
表5-1、產氫系統基本個案與變數操作範圍表 73

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