本研究為提升甲醇熱化學產氫之產率，於第一部分對白金催化劑進行實驗，以確定其對自熱重組的適用性，同時該實驗將通過改變蒸汽對甲醇之莫耳比和氧氣對甲醇之莫耳比來分析自熱重組的性能，此外，將比較甲醇自熱重組及部分氧化之優劣。第二部分，將鎳銅催化劑置於噴霧反應器中進行甲醇部分氧化反應並觀察其性能，並於實驗結果的基礎上使用最佳化反應曲面法分析結果趨勢及最佳組。隨後，通過方差分析探討操作條件的重要性和適用性。最後，將本研究的鎳銅催化劑與白金催化劑進行比較。
第一部分旨在使用白金催化劑以冷啟動的方式通過噴霧進行甲醇自熱重組，主要關注操作條件對製氫及甲醇轉化之影響，同時，進行甲醇的甲醇自熱重組和部分氧化的比較。其部分氧化之結果表明在氧氣對甲醇之莫耳比為0.7時，可以獲得最高的氫氣及一氧化碳濃度，甲醇轉化率達到100%。但通過自熱重組，於相同條件下並將蒸汽對甲醇之莫耳比調整為1.5的甲醇轉化率卻是60%。然而，值得一提的是在蒸汽對甲醇之莫耳比為0.5時，觀察到隨著氧氣對甲醇之莫耳比的增加，甲醇轉化率高達100%，並氫氣產率高於部分氧化。結果表明，隨著蒸汽對甲醇之莫耳比的降低和氧氣對甲醇之莫耳比的提高，甲醇轉化率及反應溫度都會顯著提高。總體而言，在蒸汽對甲醇之莫耳比為0.5和氧氣對甲醇之莫耳比為0.7之條件下，自熱重組擁有最高氫氣產率1.697 mol (mol CH3OH)-1。
在第二部分中，為了降低實驗成本，將使用新型的鎳銅催化劑進行甲醇部分氧化產生氫氣，並透過反應曲面法中的Box-Behnken設計實現實驗設計的優化，其中鎳銅催化劑相較於其他貴金屬催化劑擁有更低的價格，而Box-Behnken設計可以有效的減少實驗組數進而降低成本。實驗前，以氧氣對甲醇莫爾比（0.5-0.7）、預熱溫度（150-250 °C）及鎳的重量百分比（10-30%）作為實驗設計的變量因子。實驗後，透過反應曲面法分析出最佳組(氧氣對甲醇莫爾比為0.5、預熱溫度為150 °C及鎳的重量百分比為10%)並通過方差分析（ANOVA）分析出氧氣對甲醇莫耳比擁有最好的重要性及適用性。對催化劑進行分析SEM、EDS及XRD，分別探討催化劑的表面結構、元素組成及物理結構。結果表明，在所有操作條件下，甲醇轉化率皆為100%而氫氣產率最高為2 mol (mol CH3OH)-1。此外，發現當鎳的重量百分比越高，反應活性越趨向高溫。

Nowadays, the development of alternative energy is regarded as a key solution to reduce the environmental issue. Hydrogen is one of the promising clean energy applied in power generation and transport. In particular, due to the considerable progress in the development of fuel cells, the researches of hydrogen production applied in vehicles, portable devices and small-scale power plants have attracted much attention recently. Concerning to hydrogen production, the thermochemical methods have been widely used, such as water gas shift reaction (WGSR), steam reforming (SR), partial oxidation (POX), and autothermal reforming (ATR). Therefore, the first part of this study conducts an experimental investigation into the Pt/Al2O3 catalyst to figure out its suitability for ATR, while the experiment will analyze the performance of ATR by altering steam-to-methanol and oxygen-to-methanol molar ratios. In addition, the comparison between methanol ATR and POX will be explored. In the second part of this study, the Ni-Cu/Al2O3 catalyst is used under a spray reactor for POM and observe the performance. The operating conditions of O2/C ratio, preheating temperature, and wt% of Ni are considered in BBD of RSM. After experiment, the impact of each operating condition will be explored on the results. Base on experiment result, the optimization case was analyzed by BBD of RSM and the significance and suitability of operating conditions by ANOVA. Finally, the catalyst of this study will be compared with h-BN-Pt/Al2O3 (Green Hydrotech Inc.).
The first part aims to perform autothermal reforming (ATR) of methanol by sprays via the h-BN Pt catalyst with a cold start, mainly focusing on the effects of operating conditions on hydrogen production and methanol conversion. Meanwhile, the comparison between ATR and POX of methanol is also carried out. The results of POM indicate that the highest H2 and CO concentrations are obtained at the air-to-methanol molar ratio (O2/C) of 0.7, and the CH3OH conversion can reach 100%. However, through the ATR process, the methanol conversion reaches 60% at O2/C=0.7 with steam-to-methanol molar ratio (S/C) of 1.5. At S/C=0.5, it is observed that the CH3OH conversion is up to 100% with increasing the O2/C ratio, and the H2 yield is higher than that of POM. The effects of S/C and O2/C ratios on ATR indicate that the CH3OH conversion and reaction temperature are significantly increased with decreasing the S/C ratio and increasing the O2/C ratio. Overall, the highest H2 yield from ATR is 1.697 mol (mol CH3OH)-1 and occurs at S/C =0.5 and O2/C=0.7.
In second part, the Ni-Cu/Al2O3 catalyst and Box-Behnken design (BBD) of response surface methodology (RSM) are used for reducing experiment cost because Ni-Cu/Al2O3 is cheaper than other noble metal catalyst and BBD could decrease experimental cases to reduce cost. Therefore, a novel Ni-Cu/Al2O3 catalyst is used for hydrogen production. Partial oxidation of methanol is selected as the main thermochemical reaction for hydrogen production and the reactor is installed with a spray. BBD is utilized not only for the experiments but also to achieve the optimization of process design. The operating conditions varied for the experimental design are O2/C ratio (0.5-0.7), preheating temperature (150-250 °C), and wt% of Ni (10-30%). The catalyst is analyzed under SEM, EDS, and XRD to explore its surface structure, elemental composition, and physical structure respectively. Results show that the methanol conversions are 100% for all operating conditions, while the reaction temperature ranges from 160 to 750 °C. In addition, the significance and suitability of operating conditions are analyzed by ANOVA. The results of RSM indicate that the highest hydrogen yield is 2 mol (mol CH3OH)-1 under the operating conditions of O2/C=0.5, preheating temperature=150 °C, and 10 wt% of Ni. Compared with h-BN-Pt/Al2O3 catalyst, the Ni¬¬-Cu/Al2O3 catalyst has a higher activity for H2 production. In ANOVA, the O2/C ratio is the most influential factor in the H2 yield. Moreover, the interaction of the O2/C ratio and Ni content is sound, and this result explains that changing Ni content in the catalyst will affect the trend of H2 yield under each O2/C.

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