本研究以數值模擬形式，進行有無吸附助效甲烷蒸汽重組之速度分析，針對不同操作條件找出何種反應器之平均速度與滯留時間相對誤差較大，並且在吸附助效反應器中找出何種水碳比到達操作終止時間其氧化鈣轉化率較佳。
有無吸附助效甲烷蒸汽重組之速度分析的部份，藉由改變不同操作條件，探討何種反應器的滯留時間相對誤差較大，其中估算值為入口速度推導之滯留時間，而實際值為氣體於觸媒床之真實滯留時間。數值模擬結果顯示當水碳比越小、溫度越高、WHSV越小時，滯留時間之誤差越大，其中水碳比2，溫度為800°C，WHSV為5 h-1之甲烷蒸汽重組反應器於觸媒床之滯留時間的誤差提升至52.80%，而吸附助效反應器之平均速度分析，前三階段與甲烷蒸汽重組反應器相同(分別為擴散控制、溫度控制、重組反應控制)，最後再加上吸附反應控制，而此階段是所有區域中誤差最大的，滯留時間之誤差來到39.75%，而滯留時間的誤差越大，表示反應物於觸媒床的化學反應時間越短，產氫效能較差。
吸附助效反應器中氧化鈣轉化率的部份，藉由改變水碳比觀測其氧化鈣轉化率與二氧化碳吸附量，數值模擬結果顯示，當水碳比越高其終止時間會延後且整體氧化鈣轉化率值越高，二氧化碳吸附量也越多，其中水碳比5之操作終止時間延後至1753秒，整體氧化鈣轉化率提升至56.85%，二氧化碳吸附量為17.85克。

In this study, the velocity analysis of methane steam reforming with or without sorption enhancement by numerical simulation. According to different operating conditions, it is found that which reactor has a larger relative error in the average velocity and residence time, and it is found that the S/C ratio reaches the operation termination time in the sorption enhanced reactor, which has the better calcium oxide conversion rate.
In the part of velocity analysis of methane steam reforming with or without sorption enhancement, by varying operating conditions, it is discussed which reactor has a larger relative error of the residence time. The estimated value is the residence time derived from the inlet velocity, while the actual value is the real residence time of the gas in the catalyst bed. The numerical simulation results show that the error of the residence time is larger when the S/C ratio is smaller, the temperature is higher, and the WHSV is smaller. For the methane steam reforming reactor with S/C ratio of 2, the temperature of 800°C, and the WHSV of 5 h-1, the error of the residence time in the catalyst bed increased to 52.80%, and the average velocity analysis of the sorption enhanced reactor showed that the first three stages were the same as the methane steam reforming reactor (respectively, diffusion control, temperature control, and reforming reaction control), and the Region IV is the sorption reaction control, the region has the largest relative error among all regions, the error of residence time up to 39.75%. The larger the error of residence time, the shorter the chemical reaction time of reactants in the catalyst bed, and the worse the hydrogen production efficiency.
In the part of the conversion rate of calcium oxide in the sorption enhanced reactor, the conversion rate of calcium oxide and the amount of carbon dioxide adsorption are observed by changing the S/C ratio. The numerical simulation results show that the higher the S/C ratio, the longer the termination time, the higher the overall calcium oxide conversion rate, and the more carbon dioxide adsorption. The operation termination time of the S/C ratio of 5 is delayed to 1753 seconds, the overall calcium oxide conversion rate is increased to 56.85%, and the carbon dioxide adsorption amount is 17.85 grams.

摘要 i
Abstract ii
目錄 iv
表目錄 vii
圖目錄 ix
符號說明 xii
第一章 緒論 1
1.1 前言 1
1.2 產氫方式 3
1.2.1 蒸汽重組(Steam reforming, SR) 3
1.2.2 部分氧化(Partial oxidation, POX) 6
1.2.3 自熱重組(Autothermal reforming, ATR) 8
1.3 文獻回顧 9
1.3.1 甲烷蒸汽重組 9
1.3.2 氧化鈣吸附反應 10
1.3.3 吸附助效甲烷蒸汽重組反應 12
1.3.4 反應器逆流(RF)操作 13
1.4 研究目的 14
第二章 數學模式與數值方法 16
2.1 反應器 16
2.1.1 甲烷蒸汽重組之反應器模型 16
2.1.2 吸附助效甲烷蒸汽重組之反應器模型 18
2.2 基本假設 20
2.3 統御方程式 21
2.3.1 質量守恆方程式 21
2.3.2 動量守恆方程式 22
2.3.3 能量守恆方程式 23
2.3.4 成分方程式 24
2.4 化學反應式 24
2.4.1 甲烷蒸汽重組反應模式 25
2.4.2 氧化鈣吸附反應模式 27
2.5 邊界條件 30
2.6 數值方法 31
第三章 結果與討論 32
3.1 模型驗證 32
3.1.1 甲烷蒸汽重組器(MSR) 32
3.1.2 吸附助效甲烷蒸汽重組器(SESMR) 34
3.2 操作終止條件定義 35
3.3 甲烷蒸汽重組器之反應器內流速分析 36
3.3.1 不同水碳比(S/C= 2~5) 36
3.3.2 不同溫度(T = 600~800℃) 48
3.3.3 不同WHSV(5 h-1、10 h-1、20 h-1) 60
3.3.4 不同操作變因下的實際速度、估算速度與滯留時間分析 70
3.4 吸附助效甲烷蒸汽重組器之反應器內流速分析 82
3.4.1 平均速度分析 85
3.4.2 平均溫度分析 89
3.4.3 反應速率分析 92
3.4.4 平均分子量與莫耳濃度分析 95
3.4.5 質量流率與氧化鈣轉化率分析 99
3.4.6 實際速度、估算速度與滯留時間分析 102
3.5 SESMR於不同水碳比之二氧化碳吸附量與氧化鈣轉化率 103
3.6 SESMR於不同水碳比之甲烷轉化率與氫產量 112
3.7 SESMR之同溫反轉 114
第四章 結論與未來建議 116
4.1 結論 116
4.2 未來建議 117
參考文獻 118

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