本論文使用計算流體力學(Computational Fluid Dynamics, CFD)軟體FLUENT，完成甲烷蒸氣重組製氫程序中二次重組反應器，管球直徑比(N)為4之模擬，包括球形與圓柱形觸媒。本論文並應用整合式多目標最佳化(Integrated Optimization System)，包括實驗設計法(Design Of Experiment, DOE)、CFD模擬、反應表面法(Response Surface Method)以及基因演算法(Genetic Algorithm, GA)，考慮單位長度觸媒床之壓損最小化與氫氣生成速率最大化之雙目標函數，完成二次重組反應器之觸媒設計最佳化設計。
球形與圓柱形觸媒最佳化設計結果均顯示，觸媒孔隙直徑對各目標函數之影響均很小，觸媒直徑之改變會產生兩個目標函數間之相互妥協現象。圓柱形觸媒最佳化設計結果顯示，最佳解使用大單孔觸媒或四孔觸媒之設計。使用大單孔觸媒之設計時，觸媒孔隙直徑應使用較大值，約1 μm，觸媒直徑則應介於0.01~0.013 m；使用四孔觸媒之設計時，觸媒孔隙直徑無特別重要性，觸媒直徑則應介於0.006~0.008 m。

In this thesis, the packed bed secondary reformer in the industrial hydrogen generation process is simulated using Computational Fluid Dynamics (CFD) for the reactor with tube-to-particle diameter ratio of 4 and both spherical and cylindrical shape of catalysts. An integrated optimization scheme, involving design of experiment, computational fluid dynamics simulation, response surface model, and genetic algorithm, is further appled for the mutiobjective optimization of catalyst design. The objective functions are pressure drop and hydrogen generation rate.
For both spherical and cylindrical catalysts, the objective functions are not sensitive to the catalyst pore diameter; however, the catalyst particle diameter shows trade-off relation on the two objective functions.
The optimization results reveal that the one-big-hole or the four-hole designs should be used for the cylindrical catalysts. For the one-big hole cylindrical catalyst, larger catalyst pore diameter, around 1 μm, and the catalyst particle diameter between 0.01 m and 0.013 m should be used. For the four hole cylindrical catalyst, the catalyst pore diameter is of no significance, but the catalyst particle diameter should be in the range of 0.006~0.008 m.

中文摘要	I
英文摘要	II
目錄	III
圖目錄	VI
表目錄	IX
第一章 前言	1
第二章 文獻回顧	3
2.1 填充床式反應器之計算流體力學模擬與觸媒設計	3
2.2 氫氣生成	6
2.3 整合式多目標最佳化	8
第三章 計算流體力學模式之建立	9
3.1 系統配置與網格建立	9
3.2 理論模式	14
3.2.1 基本統制方程式	14
3.2.2 混合物性模式	15
3.2.2.1 混合物黏度	15
3.2.2.2 混合物熱傳導係數	16
3.2.2.3 混合物質傳係數	17
3.2.3 化學反應和反應動力模式	18
3.2.4 紊流模式	21
3.2.5 紊流壁面處理	23
3.3 數值方法	25
3.3.1 離散方法	25
3.3.2 速度-壓力耦合方法	25
3.3.3 收斂準則與迭代參數	26
第四章 甲烷蒸氣重組反應器之計算流體力學模擬	27
4.1 甲烷蒸氣重組反應器	27
4.1.1 邊界條件設定	30
4.2 球型觸媒反應器模擬	31
4.2.1 網格無關化分析	31
4.2.2 邊界條件與其合理性	34
4.2.3 模擬結果	38
4.2.3.1 對稱性邊界條件之驗證	39
4.2.3.2 觸媒孔隙直徑對球形觸媒反應器之影響	42
4.2.3.3 觸媒直徑對球形觸媒反應器之影響	46
4.3 圓柱型觸媒反應器模擬	50
4.3.1 網格無關化分析	50
4.3.2 模擬結果	50
4.3.2.1 觸媒孔徑對圓柱形觸媒反應器之影響	52
4.3.2.1.1 實心圓柱與單孔圓柱之比較	52
4.3.2.1.2 小四孔圓柱與四孔圓柱之比較	54
4.3.2.2 觸媒直徑對圓柱形觸媒反應器之影響	56
4.3.2.2.1 實心圓柱與單孔圓柱之比較	56
4.3.2.3 單孔圓柱與大單孔圓柱之比較	58
第五章 甲烷蒸氣重組反應器觸媒設計最佳化	60
5.1 整合式多目標最佳化	60
5.1.1 實驗設計法	61
5.1.2 反應表面法	61
5.1.3 基因演算法	62
5.2 球形觸媒反應器	63
5.2.1 目標函數與決策變數	63
5.2.2 實驗設計法	64
5.2.3 反應表面法	66
5.2.4 基因演算法參數決定	70
5.2.5 基因演算法最佳化結果	72
5.3 圓柱形觸媒反應器	74
5.3.1 目標函數與決策變數	74
5.3.2 實驗設計法	75
5.3.3 反應表面法	77
5.3.4 基因演算法參數決定	84
5.3.5 基因演算法	86
第六章 結論	89
符號說明	91
參考文獻	96
附錄	101

圖2.1碳氫化合物製氫製程(Bartholomew與Farrauto, 2006)	7
圖3.1圓柱形觸媒孔洞分佈位置	11
圖3.2反應器網格圖	13
圖3.3反應器網格示意圖	13
圖3.4近壁面處流動結構圖(Fluent, 2005)	23
圖3.5壁面函數與近壁模型示意圖(Fluent, 2005)	24
圖4.1反應器截面	32
圖4.2球型觸媒反應器內部徑向截線速度分佈	33
圖4.3球型觸媒反應器徑向截線速度分佈-近壁處	33
圖4.4觸媒內部設定為固體與多孔性介質之速度分佈	36
圖4.5觸媒內部設定為固體與多孔性介質之壓力分佈	36
圖4.6觸媒內部設定為固體與多孔性介質之 分佈	37
圖4.7 Theta1與Tehta5之速度、溫度、氫氣質量分率圖	40
圖4.8 Theta2與Tehta4之速度、溫度、氫氣質量分率圖	41
圖4.9球形觸媒反應器觸媒孔隙直徑對速度之影響	43
圖4.10球形觸媒反應器觸媒孔隙直徑對溫度之影響	43
圖4.11球形觸媒反應器觸媒孔隙直徑對甲烷質量分率之影響	44
圖4.12球形觸媒反應器觸媒孔隙直徑對一氧化碳質量分率之影響	44
圖4.13球形觸媒反應器觸媒孔隙直徑對氫氣質量分率之影響	45
圖4.14球形觸媒反應器觸媒直徑對速度影響	47
圖4.15球形觸媒反應器觸媒直徑對溫度影響	47
圖4.16球形觸媒反應器觸媒直徑對甲烷質量分率影響	48
圖4.17球形觸媒反應器觸媒直徑對一氧化碳質量分率影響	48
圖4.18球形觸媒反應器觸媒直徑對氫氣質量分率影響	49
圖4.19圓柱形觸媒床之截面	50
圖4.20圓柱形觸媒反應器觸媒孔隙直徑與孔洞對速度影響	53
圖4.21圓柱形觸媒反應器觸媒孔隙直徑與孔洞對溫度影響	53
圖4.22圓柱形觸媒反應器觸媒孔隙直徑與孔洞對氫氣質量分率影響	53
圖4.23圓柱形觸媒反應器觸媒孔隙直徑與孔洞大小對速度影響	55
圖4.24圓柱形觸媒反應器觸媒孔隙直徑與孔洞大小對溫度影響	55
圖4.25圓柱形觸媒反應器觸媒孔隙直徑與孔洞大小對氫氣質量分率影響	55
圖4.26圓柱形觸媒反應器觸媒直徑與孔洞對速度影響	57
圖4.27圓柱形觸媒反應器觸媒直徑與孔洞對溫度影響	57
圖4.28圓柱形觸媒反應器觸媒直徑與孔洞對氫氣質量分率影響	57
圖4.29圓柱形觸媒反應器觸媒直徑與孔洞大小對速度影響	59
圖4.30圓柱形觸媒反應器觸媒直徑與孔洞大小對溫度影響	59
圖4.31圓柱形觸媒反應器觸媒直徑與孔洞大小對氫氣質量分率影響	59
圖5.1整合式最佳化系統	60
圖5.2 Pareto圖(OF1，OF2和OF3均求最小化)	62
圖5.3球形觸媒反應器實驗設計點空間分佈	65
圖5.4球形觸媒反應器目標函數之模擬值與迴歸結果比較	69
圖5.5球形觸媒反應器RSM圖	69
圖5.6改變基因演算法參數之最佳解分佈	71
圖5.7球形觸媒反應器之Pareto圖	72
圖5.8球形觸媒反應器最佳解之變數-目標函數分佈	73
圖5.9圓柱形觸媒反應器實驗設計點空間分佈	76
圖5.10圓柱形觸媒反應器目標函數之模擬值與迴歸結果比較	80
圖5.11 圓柱形觸媒目標函數OF1之RSM圖	81
圖5.12 圓柱形觸媒OF2之RSM圖	82
圖5.13 圓柱形觸媒OF3之RSM圖	83
圖5.14圓柱形觸媒改變基因演算法參數之最佳解分佈	85
圖5.15圓柱形觸媒反應器之Pareto圖	87
圖5.16圓柱形觸媒反應器最佳解之變數-目標函數分佈	88
圖A.1球形觸媒標號	101
圖A.2圓柱形觸媒標號	102

表3.1黏度參數	15
表3.2熱傳導係數參數	16
表3.3原子與官能基擴散體積增量表	17
表3.4甲烷製氫系統反應速率常數之參數值	20
表3.5甲烷製氫系統吸附係數之參數值	20
表3.6 離散方法與鬆弛因子設定	26
表3.7 收斂準則	26
表4.1反應器進料數據	28
表4.2 模擬個案	29
表4.3邊界條件	30
表4.4網格無關化個案網格條件	32
表4.5觸媒內部與觸媒表面為固體與壁個案之邊界條件	35
表4.6觸媒內部與觸媒表面設定為多孔性介質與內部面個案之邊界條件	35
表4.7球形觸媒反應器壓降與反應程度	38
表4.8圓柱形觸媒反應器之壓降與反應程度	51
表5.1球形觸媒反應器決策變數改變範圍	64
表5.2球形觸媒反應器實驗設計結果	65
表5.3球形觸媒模擬個案之目標函數值	67
表5.4目標函數之參考值與迴歸係數結果	67
表5.5球形觸媒反應器迴歸結果統計分析	68
表5.6 基因演算法參數值改變之影響	70
表5.7球形觸媒反應器之最佳化部分解	72
表5.8圓柱形觸媒反應器決策變數改變範圍	75
表5.9圓柱形觸媒反應器實驗設計結果	76
表5.10 圓柱形觸媒模擬個案之目標函數值	78
表5.11目標函數之參考值與迴歸係數結果	78
表5.12圓柱形觸媒反應器迴歸結果統計分析	78
表5.13基因演算法參數值改變之影響	84
表5.14圓柱形觸媒反應器部分解之變數內容	87
表A.1球型觸媒球心位置	101
表A.2圓柱形觸媒孔洞座標位置	102
表A.3圓柱形觸媒繪製方式	103
表A.4球形觸媒基因演算法結果	104
表A.5圓柱形觸媒基因演算法結果	105

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