本文以數值模擬方式探討CO甲烷化反應器的性能，及整合甲醇蒸氣重組、CO去除及燃燒供熱的小型管狀反應器之產氫性能。在使用Ni/Al2O3為觸媒的CO甲烷化反應器中，本文分析在等溫過程中，溫度、流量、觸媒填充長度及入口氣體成份等操作參數對反應器性能的影響，模擬結果顯示在適當操作條件下，CO甲烷化反應器的CO轉換效率及CH4選擇性都可達到99%以上。結果也顯示對一固定的入口成份及觸媒量，則存在一入口流量使得CO轉換率及CH4選擇性達到最高值。溫度高低對於整體性能影響也非常大，其中在成份變化過程中，H2/CO之莫爾比越高對於CO轉換效率越佳。但在有H2O添加到入口氣體時，當H2O/CO莫爾比值越大將不利於CO甲烷化反應。
在整合甲醇重組、甲醇觸媒燃燒及CO去除的管狀甲醇重組器中，內管的甲醇蒸氣重組使用CuO/ZnO/Al2O3觸媒，外管的Pt/Al2O3觸媒用於甲醇觸媒燃燒以提供重組所需熱量。甲醇蒸氣重組後的合成氣約有1~5 % CO，本文利用CO甲烷化降低其CO濃度，使用的觸媒為Ni/Al2O3 。本文分析甲醇-水流量、甲醇-氧氣流量、CO甲烷化觸媒填充長度及反應器外管壁熱損失等操作參數對反應器性能及各成分濃度影響。由模擬結果可知在適當的操作條件下，反應器的甲醇轉換率可大於98%且CO轉換率也可大於95%。結果也顯示對於一固定的甲醇-水流量及CO甲烷化觸媒量，則存在一最佳的甲醇-氧氣流量能使甲醇轉換率及CO轉換率達到最佳。對固定甲醇-水流量及甲醇-氧氣流量的條件下，存在有最佳的CO甲烷化觸媒填充長度。

The performances for both the tube reactor for CO methanation and the small tubular reactor of methanol-steam reforming for hydrogen production are investigated numerically in this study. For the CO methanator using Ni/Al2O3 as catalyst, the effects of temperature, flow rate, catalyst loading, and inlet gas composition in isothermal process are studied. The results show that both the CO conversion and the CH4 selectivity can reach 99% under optimum operating condition. For fixed catalyst loading and inlet gas composition, the result from the variation of flow rate shows that there exists a peak value of the CO conversion and CH4 selectivity. The temperature plays an important effect in the reactor performance. Furthermore, the higher molar H2/CO ratio is, the better CO conversion is. When adding H2O at inlet gas, the CO methanation reaction speed is reduced for the higher molar H2O/CO ratio.
In the tubular methanol reformer integrating with methanol reforming, CO removal, and methanol catalytic combustion, the CuO/ZnO/Al2O3 catalyst in the inner tube is used for methanol steam reforming and the Pt/Al2O3 catalyst in the outer tube is used for methanol catalytic combustion to supply the thermal energy for reforming. The reformed syngas contains about 1~5% CO, the CO methanation with Ni/Al2O3 as catalyst is used to lower the CO concentration. The effects of the operating parameters of methanol-water flow rate, methanol-oxygen flow rate, Ni/Al2O3 filling length and the heat loss from the outside wall on the reactor performance are studied. The numerical results show that under appropriate condition, the methanol conversion rate can over 98% and CO conversion can over 95%. Under the conditions that the methanol-steam flow rate and catalyst fillings are fixed, there exists a methanol-oxygen flow rate range where both the methanol conversion and CO conversion can reach the optimum value. There also exists an optimum catalyst filling length for CO methanation with higher methanol conversion and CO conversion when the methanol-water and methanol-oxygen flow rates are fixed.

第一章 緒論 9
1.1 前言 9
1.2 文獻回顧 11
1.2.1甲醇空氣燃燒之文獻回顧 11
1.2.2甲醇蒸氣重組之文獻回顧 12
1.2.3整合甲醇蒸氣重組及觸媒燃燒之文獻回顧 13
1.2.4整合重組器模擬 15
1.2.5 CO甲烷化反應之文獻 15
1.3 研究目的 18
第二章 CO甲烷化反應器及整合反應器 20
2.1 CO甲烷化反應器 20
2.2整合反應器 20
第三章 數學模式與數值方法 22
3.1 物理說明與基本假設 22
3.2 統御方程式 23
3.2.1 質量守恆方程式 23
3.2.2 動量方程式 23
3.2.3 能量方程式 24
3.2.4 物質方程式 25
3.3化學反應 25
3.3.1 甲醇蒸氣重組反應模式 25
3.2.2 甲醇觸媒燃燒反應模式 27
3.2.3 CO甲烷化反應模式 28
3.4邊界條件 28
3.4.1 CO甲烷化反應器-邊界條件 29
3.4.2 整合反應器-邊界條件 31
3.4數值方法 34
第四章 初步討論與結果 36
4.1 CO甲烷化反應器 43
4.1.1 流量對反應器性能及各成份濃度的效應 43
4.1.2溫度對反應器性能及各成份濃度的效應 48
4.1.3催化劑長度對反應器性能的效應 53
4.1.4入口成份變化對反應器性能及各成份濃度的效應 55
4.2 整合反應器 58
4.2.1甲醇-水流量對反應器性能及各成份濃度的效應 58
4.2.2甲醇-氧氣流量對反應器性能及各成份濃度的效應 66
4.2.3 CO甲烷化觸媒填充長度對反應器性能的效應 73
4.2.4反應器外管有熱損失下，對反應器性能及各成份濃度的效應 74
第五章 結論與未來發展 81
5.1 結論 81
5.1.1 CO甲烷化反應器 81
5.1.2 整合反應器 82
5.2 未來發展 83
參考文獻 84

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