本研究使用以氫氧燃燒作為熱源之整合式甲醇蒸汽重組反應器，並在觸媒中心放置一熱管，以改善觸媒床內縱向不均溫之現象。本實驗設計兩種不同長寬比之反應器，以比較反應器內徑對於觸媒均溫性、甲醇轉化率及CO濃度之影響，同時比較兩種反應器在觸媒填充長度減半及破壞熱管使其失效後對於反應器性能的影響，其中觸媒填充長度減半後，以氧化鋁球填滿反應器後段空間。實驗在固定水與甲醇進料比S/C=1.5、不同溫度及不同進料流量(Qin)下進行。實驗結果發現，高長寬比之反應器在使用有效熱管、Qin=0.3 ml/min，甲醇轉化率可達100%、CO濃度1.26%，而相同觸媒填充重量、實驗條件下，低長寬比之反應器僅達88.5%甲醇轉化率、CO濃度1.3%，即高長寬比之反應器對於提高甲醇轉化率及降低CO濃度有正向效果，其因高長寬比反應器改善反應器徑向溫差，而熱管改善反應器縱向溫差。減少反應器內部觸媒填充長度或破壞熱管，兩者實驗條件皆會使兩種長寬比之反應器降低甲醇轉化率及提高CO濃度。各項實驗皆進行重複性驗證，觸媒床溫度及甲醇轉化率皆有良好的重複性，但CO濃度則重複性較差。

This study investigates the performance of an integrated packed-bed catalytic methanol steam-reformer heated by catalytic hydrogen combustion. A heat pipe is embedded in the center of the packed-bed reformer to improve the uniformity of the axial temperature of the reformer. Two systems with different aspect ratios are tested to compare the effect of reformer geometry on the catalyst temperature distribution, methanol conversion and CO concentration. In addition, the effects of halved catalyst-packed length and the ineffectiveness of the heat pipe are examined. The rear space of the reactor with halved catalyst-packed length is filled with inactive alumina spheres. The experiments are conducted under a fixed water/methanol ratio (S/C) of 1.5 but different average temperatures and methanol/water feed rates (Qin). The experimental results show that the high-aspect-ratio reformer can yield 100% methanol conversion and a product of 1.26% CO concentration using the heat pipe under a flow rate of Qin=0.3 ml/min. Under the same catalyst-packed weight and experimental conditions, the low-aspect-ratio reformer only yields 88.5% methanol conversion and 1.3% CO concentration. It means that high-aspect-ratio reformer favors methanol conversion and reduces CO concentration due to improved radial temperature uniformity. The inserted heat pipe further improves the axial temperature uniformity. Furthermore, if the catalyst-packed length is reduced or the heat pipe is deactivated, the methanol conversion and CO concentration are deteriorated for both reformers. All experiments are tested twice with good repeatability for the catalyst temperature distribution and methanol conversion. However, the repeatability for CO concentration is not as good.

摘要 ii
Abstract iii
致謝 iv
目錄 v
表目錄 viii
圖目錄 ix
符號表 xiv
一、 緒論 1
1.1前言 1
1.2 文獻回顧 6
1.2.1 甲醇製氫反應機制 6
1.2.1.1 甲醇製氫方法 6
1.2.2.2 甲醇蒸汽重組反應機制 7
1.2.2 甲醇蒸汽重組反應器 12
1.2.2.1 甲醇蒸汽重組反應器類別 12
1.2.2.2 甲醇蒸汽重組之熱傳限制及影響 12
1.2.2.3 甲醇蒸汽重組反應器設計 19
1.2.2.4 放置熱管之化學反應器 27
1.3研究動機及目的 34
二、研究方法 35
2.1 實驗配置與流程 35
2.2 實驗儀器 36
2.2.1 蠕動泵浦 36
2.2.2 溫度紀錄 36
2.2.3 氣體檢測系統 37
2.3 整合式重組反應器 39
2.3.1 反應器設計及尺寸 39
2.3.2 觸媒填充方法及熱管放置 43
2.3.3 溫度測量 46
2.3.4 觸媒還原 47
2.4 實驗參數及實驗條件 48
三、實驗結果與討論 50
3.1 有效熱管之整合式反應器測試 50
3.1.1 低長寬比之反應器測試 50
3.1.1.2 低長寬比反應器擺放角度之影響 58
3.1.1.3 低長寬比反應器重複性驗證 61
3.1.2 高長寬之反應器測試 68
3.1.2.1 反應器長寬比之影響 68
3.1.2.2 高長寬比之反應器觸媒填充長度之影響 70
3.1.2.3 高長寬比之反應器重複性驗證 77
3.2 無效熱管之整合式反應器測試 84
3.2.1低長寬比之反應器無效熱管測試 84
3.2.2高長寬比之反應器無效熱管測試 91
四、結論 97
參考文獻 99

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