臺灣博碩士論文加值系統

氫氣工廠蒸汽重組爐是一種提供熱量使天然氣或液化石油氣藉由觸媒作用轉換成氫氣的燃燒裝置，它被使用在石化工業以產生氫氣；發生於觸媒管(又稱輻射管)內的重組過程是一種吸熱反應，重組爐內的燃燒過程提供熱量以維持觸媒管內的重組反應；觸媒管溫度控制為重組爐設計之基本要求，因為溫度必須維持在觸媒活性最大但觸媒管損壞程度最小的範圍；蒸汽重組爐操作時，觸媒管承受之應力接近其金屬材料之極限應力，當觸媒管進行加熱/冷卻等溫度變化時，應力會暫時地增加並加速潛變的傷害，如能避免溫度急遽變化，就能延長觸媒管壽命。
由於重組爐的操作溫度可達900oC以上，且現今計算工具與物理模式以及數值方法快速發展，使得數值模擬分析相較於實驗量測更為方便運用，因此，本研究針對一工業尺寸蒸汽甲烷重組爐熱流場進行詳細的數值模擬分析，探討影響蒸汽重組爐觸媒管使用壽命之因素，探討參數包含：(1)水蒸汽莫爾分率(YH2O)之影響、(2)重組爐觸媒管數量、尺寸與排列方式之影響、(3)燃燒器操作方式之影響、以及(4)重組爐幾何外形之影響等，期透過本研究以瞭解重組爐操作參數對於重組爐觸媒管溫度與壓力分佈之影響，並提升重組爐操作效能與觸媒管使用壽命；由研究結果發現，週期性邊界條件模型所解得之溫度與氫氣莫爾分率比實驗值低很多，且所解得之爐管內平均壓力比實際模型所解得之壓力低很多，可能造成爐管壽命高估，導致低估設備運轉時的風險，而實際模型所解得之氫氣平均莫爾分率約為0.67，非常接近實驗值；每枝觸媒管之壽命不同，靠近中間偏下游處，爐管壽命較長；相對而言，靠近中間偏上游處，爐管壽命較短；當YH2O=0.5時，重組爐觸媒管內之反應物趨近於化學計量混合物，觸媒管壽命最長，在另一方面，偏離化學計量混合物時，例如YH2O=0.1與0.7，觸媒管壽命較短；簡化模型觸媒管內部壓力較大，但其爐管溫度較低，因此，有較長的觸媒管壽命，在另一方面，雖然實際模型觸媒管內部壓力較小，但因其爐管溫度較高，因此，觸媒管壽命仍比簡化模型之觸媒管壽命短；燃燒器關閉對於所有的觸媒管壽命均有提升作用，尤其是在燃燒器關閉處的相對爐管之壽命提升越多，燃燒器關閉越多，觸媒管壽命提升越多，其缺點為氫氣產量會減少；重組爐爐頂高度升高對於觸媒管壽命有提升作用，重組爐爐頂位置越高，觸媒管壽命提升越多。
關鍵詞：氫，蒸汽重組爐，觸媒管，使用壽命

Abstract
A steam reformer of a hydrogen plant is a device that supplies heat to convert the natural gas or liquid petroleum gas into hydrogen via catalysts. It has often been used in the petrochemical industry to produce hydrogen. The reforming process in a catalyst tube is an endothermic reaction. The combustion process in a reformer provides heat to maintain the reforming reaction in a catalyst tube. Control of the catalyst tube temperature is a fundamental demand of the reformer design because the tube temperature must be maintained in a range that the catalysts have high activity and the tube has minor damage.
Because of the high temperature in a steam reformer (>900oC), the numerical simulation is preferred in comparison with the experimental measurement due to the rapid development in computer science and technology, as well as the improvements in physical models and numerical methods. In this research, the transport and chemical reaction in an industrial-scale steam methane reformer are simulated using computational fluid dynamics (CFD). Five factors influencing the service life of a reformer tube are discussed: (1) the mole fraction of steam (YH2O), (2) number, size and arrangement of catalyst tubes, (3) on/off manner of burners, and (4) reformer geometry. The purpose of this research is to investigate the influence of the above factors on the temperature and pressure distributions of a reformer tube, and thus to make it possible to improve the performance and service life of a steam reformer. It is found that using the periodic boundary conditions, the temperature and hydrogen yield obtained are much lower than the experimental values, and the pressures on the inner surface using the periodic boundary conditions are much lower than those using the real model, which may result in overestimating the service life of a catalytic tube and underestimating the risk of reformer operation. The average hydrogen mole fraction at the reformer tube outlet using the real model is 0.67, which is very close to the experimental value. Each catalyst tube has individual service life. The catalyst tubes in the middle- or down-stream regions have longer service lives while those in the middle- or up-stream regions have longer service lives. When YH2O=0.5, the reactants in the catalyst tubes approach stoichiometric mixtures and the catalyst tubes have longest service lives. On the other hand, when the reactants in the catalyst tubes deviate from stoichiometric mixtures, the catalyst tubes have shorter service lives. The simplified model has higher pressures inside the catalyst tubes, lower tube wall temperatures and longer tube service lives. On the other hand, the real model has lower pressures inside the catalyst tubes, higher tube wall temperatures and shorter tube service lives. Closing some burners is beneficial to the enhancement of tube service lives, especially for the tubes in the corresponding regions of burner off. The more the burners are closed, the longer the tube service life will be. The main drawback of burner off is the decrease of hydrogen yield. Raising the reformer roof is beneficial to the enhancement of tube service lives. The tube service life increases as the shifted height of the reformer roof increases.

Keywords : Hydrogen, Steam Reformer, Catalyst Tube, Service Life

摘要......i
Abstract......iii
誌謝......vi
目錄......vii
表目錄......ix
圖目錄......x
符號說明......xiii
第一章 緒論......1
1.1 研究背景......1
1.2 重要參考文獻評述......5
1.2.1 重組爐數值模擬分析......5
1.2.2 重組爐實務探討......9
1.2.3 觸媒管破壞分析與壽命評估......11
1.3 研究目的......13
第二章 研究方法......14
2.1 數值模型......14
2.2 物理模式與數值方法......19
2.3 統御方程式......21
2.3.1 質量守恆方程式......21
2.3.2 動量方程式......21
2.3.3 k-ε Model方程式......22
2.3.4 能量方程式......24
2.3.5 DO Radiation Model方程式......24
2.3.6 Finite-Rate/Eddy-Dissipation燃燒模式......25
2.3.7 觸媒效應模擬......28
2.3.8 觸媒管剩餘壽命評估......30
2.3.9 收斂標準......34
第三章 結果與討論......35
3.1 與已知資料相比較......35
3.2 蒸汽莫爾分率之影響......42
3.3 重組爐觸媒管數量、尺寸與排列方式之影響......49
3.4 燃燒器操作方式之影響......50
3.5 重組爐幾何形狀之影響......60
第四章 結論......66
參考文獻......68

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