系統識別號 | U0002-1308201310544700 |
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DOI | 10.6846/TKU.2013.00362 |
論文名稱(中文) | 鈷硼觸媒合成條件對硼氫化鈉反應器設計之影響 |
論文名稱(英文) | Effects of Co-B catalysts synthesis conditions on sodium borohydride hydrolysis reactors design |
第三語言論文名稱 | |
校院名稱 | 淡江大學 |
系所名稱(中文) | 化學工程與材料工程學系碩士班 |
系所名稱(英文) | Department of Chemical and Materials Engineering |
外國學位學校名稱 | |
外國學位學院名稱 | |
外國學位研究所名稱 | |
學年度 | 101 |
學期 | 2 |
出版年 | 102 |
研究生(中文) | 潘泉亦 |
研究生(英文) | Chuan-Yi Pan |
學號 | 600400088 |
學位類別 | 碩士 |
語言別 | 繁體中文 |
第二語言別 | |
口試日期 | 2013-07-03 |
論文頁數 | 154頁 |
口試委員 |
指導教授
-
陳逸航(yihhang@mail.tku.edu.tw)
委員 - 錢義隆 委員 - 陳逸航 委員 - 林正嵐 |
關鍵字(中) |
鈷硼觸媒 硼氫化鈉 動力學參數 水解反應 化學還原法 |
關鍵字(英) |
Sodium borohydride Co-B catalyst Kinetic parameters Hydrolysis reaction Chemical reduction method |
第三語言關鍵字 | |
學科別分類 | |
中文摘要 |
本研究探討鈷硼觸媒合成條件與觸媒表面結構、觸媒動力學參數與硼氫化鈉水解反應器設計及操作的關係。以離子交換樹脂作為觸媒載體,硼氫化鈉為還原劑,使用離子交換法及化學還原法進行鈷硼觸媒合成。觸媒合成條件之變數為:還原溫度、還原劑濃度、還原劑pH值、還原劑添加速率以及離子交換樹脂種類。結果顯示,因水解反應及還原反應相互競爭,低還原溫度時還原速率慢,觸媒表面形成緊密排列且樹枝狀的結構,觸媒表面積較大。低溫還原之觸媒在水解產氫上有較好的表現。以L-H動力學模式進行實驗數據進行回歸,得到頻率因子、活化能、40 oC下吸附常數分別為1.17x109mol/g-min、70.65 kJ/mol、6.8 L/mol。更換載體離子交換樹脂為TP-207,以相同變數進行觸媒合成,Co-B/TP-207比上Co-B/IR-120有較高的觸媒負載量、更快的產氫速率以及更好的耐久性。以此觸媒設計硼氫化鈉產氫三相反應器尺寸,並建立數模式,分析系統之反應溫度、進料濃度、進料流率對於反應器出口氫氣流率之影響,並選定進料流率來操控出口氫氣流率。在80oC操作下,I-1至I-4觸媒中,以I-4觸媒有最大的可操作範圍。 |
英文摘要 |
The objective of this work is to study the effect of various Co-B catalyst synthesis conditions on the catalyst surface morphology and kinetic parameters. The Co/B catalyst was synthesized on IR-120/TP-207 resin surface by using ion exchange and chemical reduction method using NaBH4 as a reduction agent. The reduction conditions which were investigated here were: reduction temperature, NaBH4 concentration, pH value, NaBH4 adding flow rate and different types of resins. The result shows reduction temperature gives the most dramatic effect on surface morphology which is caused by competing reactions of reduction and hydrolysis. Low reduction temperature resulted in a slower Co/B reduction rate and made the catalyst surface denser with a branched structure. This created more surface area than higher reduction temperatures. Low reduction temperature catalyst had the better performance on NaBH4 hydrolysis reaction for hydrogen generation rate. The optimal reduction temperature of the Co-B/IR-120 is 25 oC. The L-H model was used to regress kinetic parameters from the experiment data. The frequency factor, activation energy and adsorption constant are 1.17x109 mol/g-min, 70.65 kJ/mol, and 6.8 L/mol at 40oC, respectively. Finally, the TP-207 resin was used instead of IR-120. After scanning for all catalyst synthesis conditions, the Co-B/TP-207 had the higher catalyst loading, faster hydrogen generation rate and more durability than Co-B/IR-120. A mathematical model was built to design the NaBH4 hydrolysis reactor for hydrogen generation. The operating variables of the system are: reaction temperature and NaBH4 inlet concentration, inlet flowrate. From sensitivity analysis, the dominant variable of the hydrogen generation system is NaBH4 inlet flowrate. The I-4 catalyst shows the better operability at 80oC than other Co-B/IR-120 catalyst. |
第三語言摘要 | |
論文目次 |
目錄 中文摘要 I 英文摘要 II 目錄 III 圖目錄 IX 表目錄 XV 第一章、緒論 1 1.1 背景 1 1.2 文獻回顧 4 1.2.1 硼氫化鈉應用 4 1.2.2 硼氫化鈉觸媒反應 4 1.2.3 觸媒製備方法 10 1.2.3.1 離子交換樹脂反應機制 12 1.2.3.2 化學還原法製備鈷硼觸媒之反應機制 15 1.2.4 硼氫化鈉產氫系統 17 1.3 研究動機 18 1.4 論文組織 19 第二章、實驗藥品與裝置介紹 20 2.1實驗材料 20 2.1.1 觸媒合成及硼氫化鈉產氫實驗藥品 20 2.1.2 觸媒合成及硼氫化鈉產氫實驗設備 21 2.2 實驗裝置 23 2.2.1硼氫化鈉水溶液產氫實驗裝置 23 2.3 觸媒分析鑑定 25 2.4 實驗步驟 26 2.4.1 鈷硼觸媒製備步驟 27 2.4.1.1離子交換 27 2.4.1.2鈷硼觸媒還原 28 2.5實驗數據測量 30 第三章、鈷硼觸媒製備及其製備條件分析 34 3.1系統描述 34 3.1.1離子交換變數 35 3.1.2鈷硼觸媒還原 36 3.2觸媒製備變數分析 37 3.2.1離子交換 37 3.2.1.1離子交換樹脂 37 3.2.1.2離子交換時間 38 3.2.2還原變數 39 3.2.2.1還原溫度 39 3.2.2.2還原劑濃度 41 3.2.2.3還原劑pH值 45 3.2.2.4還原劑添加速率 47 3.2.2.5螯合型離子交換樹脂TP-207還原變數 48 3.2.2.6 Co-B/IR-120與Co-B/TP-207比較 50 3.3觸媒表面組成之定性定量分析 51 3.3.1元素分析(EDS) 51 3.3.2感應耦合電漿質譜分析儀(ICP-MS) 53 3.3.3比表面積(BET) 54 3.4總結 54 第四章、觸媒動力學參數回歸 56 4.1系統描述 56 4.2觸媒動力式 58 4.3反應速率常數及吸附常數回歸 60 4.4觸媒動力學參數回歸 63 4.4.1頻率因子與活化能回歸 63 4.4.2L-H動力式之吸附常數 65 4.4.3回歸結果 67 4.4.3.1還原溫度 67 4.4.3.2還原劑濃度 67 4.4.3.3 還原pH值之影響 68 4.4.3.4還原劑添加速率之影響 68 4.4.3.5基材離子交換樹脂之影響 68 4.5結果與討論 90 4.5.1 Co-B/IR-120觸媒製備還原溫度對表面結構與動力學參數之影響 90 4.5.2 Co-B/IR-120觸媒製備還原劑濃度對表面結構與動力學參數之影響 94 4.5.3 Co-B/IR-120觸媒製備還原pH值對表面結構與動力學參數之影響 95 4.5.4 Co-B/IR-120觸媒製備還原劑添加速率對表面結構與動力學參數之影響 97 4.5.5 Co-B/TP-207觸媒 97 4.5.6 Co-B/IR-120觸媒(I-2)及Co-B/TP-207觸媒(T-2) 98 4.6觸媒適用範圍分析 100 4.7觸媒耐久性 102 4.8總結 106 五、硼氫化鈉產氫三相反應器模式建立與設計操作 108 5.1背景與系統描述 108 5.2系統模式建立 112 5.2.1系統模式假設 112 5.2.2 系統數學模式建立 112 5.3 硼氫化鈉水解反應器尺寸設計 116 5.4硼氫化鈉水解產氫系統操作模擬分析 122 5.4.1硼氫化鈉水解產氫系統操作變數分析 125 5.4.1.1操作溫度之影響 125 5.4.1.2進料濃度之影響 127 5.4.1.3進料流率之影響 129 5.4.2硼氫化鈉水解產氫系統控制結構設計 131 5.4.3硼氫化鈉水解產氫系統操作範圍分析 132 5.4.4硼氫化鈉水解產氫系統進料擾動分析 136 5.5結果與討論 139 六、結論 140 符號說明 141 參考文獻 144 附錄 149 圖目錄 圖1-1、硼氫酸根與酸催化反應機制圖 6 圖1-2、硼氫酸根與金屬觸媒催化反應機制圖 6 圖2-1、硼氫化鈉水解產氫實驗與量測裝置圖 24 圖2-2、硼氫化鈉水解產氫實驗與量測裝置圖 24 圖2-3、觸媒製備示意圖 27 圖2-4、溫度紀錄程式圖示 31 圖2-5、溫度紀錄程式操作介面 31 圖2-6、電子天秤紀錄程式圖示 32 圖2-7、電子天秤紀錄程式操作介面 32 圖3-1、(a)高溫還原觸媒示意圖(b)低溫還原觸媒示意圖 42 圖3-2、Co-B觸媒SEM圖 100000X 43 Co-B/IR-120 reduction at (a) 0oC、(b) 25oC、(c)40oC、(d) 80oC 43 圖3-3、Co-B觸媒SEM圖 50000XCo-B/IR-120 還原劑NaBH4濃度為 (a) 0.5 wt. %, (b) 5 wt. %, (c) 10wt. %, (d) 15 wt. % 44 圖3-4、還原劑濃度對觸媒負載量作圖 44 圖3-5、pH值變化對觸媒還原表面結構之示意圖(a)低 pH值, (b) 高pH值 46 圖3-6、Co-B觸媒SEM圖 46 圖3-7、Co-B觸媒還原改變還原劑添加流速(a)一次添加, (b)5 ml/min 47 圖3-8、Co-B觸媒SEM圖 49 圖3-9、EDS表面元素(a)IR-120樹脂與Co-B/ IR-120, (b)TP-207樹脂與Co-B/ TP-207 52 圖4-1、I-1觸媒反應溫度40、50、60、70、80℃氫氣累積圖 57 圖4-2、I-1觸媒反應溫度40、50、60、70、80℃L-H動力參數迴歸 62 圖4-3、反應速率常數中頻率因子及活化能之線性迴歸圖 64 圖4-4、吸附常數中焓變化(ΔH0)及熵變化(ΔS0)之線性迴歸圖 66 圖4-5、Co-B/IR-120觸媒製備還原溫度之產氫實驗氫氣累積圖操作溫度(a)40oC(b) 50oC (c)60oC (d)70oC (e)80oC 70 圖4-6、Co-B/IR-120觸媒製備還原溫度之動力學參數回歸圖操作溫度(a)40oC(b) 50oC (c)60oC (d)70oC (e)80oC 71 圖4-7、Co-B/IR-120觸媒製備還原溫度之動力學參數回歸(a)I-1, k、(b)I-1,Ka (c) I-2, k、(d)I-2,Ka (e) I-3, k、(f)I-3,Ka (g) I-4, k、(h)I-4,Ka 72 圖4-8、Co-B/IR-120觸媒產氫實驗氫氣累積圖操作溫度(a)40oC(b) 60oC (c)80oC改變製備還原劑濃度,操作溫度(d)40oC (e)60oC(f) 80oC改變製備還原之pH值 73 圖4-9、Co-B/IR-120觸媒動力學參數回歸圖操作溫度(a)40oC(b) 60oC (c)80oC改變製備還原劑濃度,操作溫度(d)40oC (e)60oC(f) 80oC改變製備還原之pH值 74 圖4-10、Co-B/IR-120觸媒製備還原劑濃度及pH值之動力學參數回歸(a)I-5, k、(b)I-5,Ka (c) I-6, k、(d)I-6,Ka (e) I-7, k、(f)I-7,Ka 75 圖4-11、Co-B/IR-120觸媒製備還原劑添加速率之產氫實驗氫氣累積圖,操作溫度(a)40oC(b) 60oC (c)80oC 76 圖4-12、Co-B/IR-120觸媒製備還原劑添加速率之動力學參數回歸圖操作溫度(a)40oC(b)60oC (c)80oC 77 圖4-13、Co-B/IR-120觸媒製備還原劑添加速率之動力學參數回歸(a)I-8, k、(b)I-8,Ka (c) I-9, k、(d)I-9,Ka 78 圖4-14、Co-B/TP-120觸媒製備還原溫度之產氫實驗氫氣累積圖操作溫度(a)40oC(b) 50oC (c)60oC (d)70oC (e)80oC 79 圖4-15、Co-B/TP-207觸媒製備還原溫度之動力學參數回歸圖操作溫度(a)40oC(b) 50oC (c)60oC (d)70oC (e)80oC 80 圖4-16、Co-B/TP-207觸媒製備還原溫度之動力學參數回歸(a)T-1, k、(b)T-1,Ka (c) T-2, k、(d)T-2,Ka (e) T-3, k、(f)T-3,Ka (g) T-4, k、(h)T-4,Ka 81 圖4-17、Co-B/TP-120觸媒產氫實驗氫氣累積圖操作溫度(a)40oC(b) 60oC (c)80oC改變製備還原劑濃度,操作溫度(d)40oC (e)60oC(f) 80oC改變製備還原之pH值 82 圖4-18、Co-B/TP-207觸媒動力學參數回歸圖操作溫度(a)40oC(b) 60oC (c)80oC改變製備還原劑濃度,操作溫度(d)40oC (e)60oC(f) 80oC改變製備還原之pH值 83 圖4-19、Co-B/TP-207觸媒製備還原劑濃度及pH值之動力學參數回歸(a)T-5, k、(b)T-5,Ka (c) T-6, k、(d)T-6,Ka (e) T-7, k、(f)T-7,Ka 84 圖4-20、Co-B/TP-207觸媒製備還原劑添加速率之產氫實驗氫氣累積圖,操作溫度(a)40oC(b) 60oC (c)80oC 85 圖4-21、Co-B/TP-207觸媒製備還原劑添加速率之動力學參數回歸圖操作溫度(a)40oC(b)60oC (c)80oC 86 圖4-22、Co-B/TP-207觸媒製備還原劑添加速率之動力學參數回歸(a)T-8, k、(b)T-8,Ka (c) T-9, k、(d)T-9,Ka 87 圖4-23、Co-B/IR-120觸媒製備還原溫度變化之水解產氫曲線圖(a)40oC (b)60oC (c)80oC 93 圖4-24、Co-B/IR-120觸媒製備還原pH值變化之水解產氫曲線圖(a)40oC (b)60oC (c)80oC 96 圖4-25、Co-B/IR-120及Co-B/TP-207觸媒進行硼氫化鈉水解產氫之氫氣累積圖,反應溫度(a)40oC(b) 50oC (c)60oC (d)70oC (e)80oC 99 圖4-26、I-1~I-4觸媒在各溫度下之產氫速率 101 圖4-27、觸媒產氫持久度測試(a)I-2觸媒, (b)T-2觸媒 104 圖4-28、觸媒產氫持久度SEM圖(a)IR-120載體 30000X (b)觸媒使用前(c)觸媒使用後(d)使用多次後(e)TP-270載體 30000X (f)觸媒使用前(g)觸媒使用後(h)使用多次後 105 圖5-1、不同類型流動模式圖 109 圖5-2、水平式反應器 110 圖5-3、直立式反應器(a)底部進料(b)頂部進料 110 圖5-4、新型式硼氫化鈉水解反應器概念性設計 111 圖5-5、硼氫化鈉水解產氫固定床反應器 112 圖5-6、WHSV(1/hr)對轉化率作圖 118 圖5-7、反應器設計參數示意圖 121 圖5-8、水解反應器內各反應物與產物對反應器觸媒量之模擬 124 圖5-9、使用I-2觸媒改變操作溫度對於氫氣流率、出口濃度、產氫速率、滯留時間、轉化率關係圖 126 圖5-10、使用I-2觸媒改變進料濃度對於氫氣流率、出口濃度、產氫速率、滯留時間、轉化率關係圖 128 圖5-11、使用I-2觸媒改變進料流率對於氫氣流率、出口濃度、產氫速率、滯留時間、轉化率關係圖 130 圖5-12、用電負荷量及氫氣需求量示意圖 131 圖5-13、硼氫化鈉水解產氫系統控制結構 132 圖5-14、進料流率限制範圍 133 圖5-15、不同觸媒進料流率操作範圍 133 圖5-16、不同觸媒改變進料流率對於氫氣流率、出口濃度、產氫速率、滯留時間、轉化率關係圖 135 圖5-17、進料流率對於燃料電池氫氣需求量關係圖 136 圖5-18、溫度擾動對進料流量變化圖 137 圖5-19進料濃度擾動對進料流量變化圖 138 圖7-1、觸媒I-2與T-2之TGA曲線 150 圖7-2、I-2觸媒XRD分析結果 151 圖7-3、T-2觸媒XRD分析結果 151 圖7-4、改變觸媒量產氫累積圖 153 圖7-5、改變硼氫化鈉濃度產氫累積圖 154 表目錄 表1-1、燃料電池應用 2 表1-2、儲氫物儲氫量比較表 4 表1-3、貴金屬觸媒文獻整理表 8 表1-4、非貴金屬觸媒文獻整理表 9 表2-1、實驗設備與儀器 22 表3-1、離子交換樹脂物性比較表 38 表3-2、IR-120/TP-207載體觸媒各變數整理表 42 表3-3、Co-B/IR-120與Co-B/TP-207觸媒比較表 50 表3-4、Co-B/IR-120表面元素分析 52 表3-5、Co-B/TP-207表面元素分析 52 表3-6、Co與B含量 53 表3-7、觸媒比表面積表格 54 表4-1、I-1觸媒操作溫度對反應速率常數及吸附常數迴歸表 62 表4-2、Co-B/IR-120觸媒製備條件之動力學參數迴歸表 88 表4-3、Co-B/TP-207觸媒製備條件之動力學參數迴歸表 89 表4-4、Co-B/IR-120觸媒製備還原溫度改變之動力學參數表 91 表4-5、Co-B/IR-120觸媒製備還原劑濃度改變之動力學參數表 94 表4-6、Co-B/IR-120觸媒製備還原pH值變化之動力學參數表 95 表4-7、Co-B/IR-120觸媒製備還原劑添加速率之動力學參數表 97 表4-8、Co-B/IR-120及Co-B/TP-207觸媒動力學參數表 100 |
參考文獻 |
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