摘要
題目:發展氧化錳觸媒於高效能過氧化氫單基推進器
研究生:黎友倫
指導教授:趙怡欽 博士
關鍵字:高效能過氧化氫、單基推進器、氧化錳觸媒

太空科技代表國家的國力及科學的水平，為各國爭相開發之領域，衛星的發展也因此不斷的創新，近年來科技的進展、環保意識的抬頭、衛星的微小化與綠色、低環境衝擊且無毒性的推進方式受到重視，用於衛星推進用途的高濃度過氧化氫再度獲得重視。
高效能過氧化氫單基推進器中的核心關鍵便是高濃度過氧化氫與其分解觸媒，由參考文獻可以得知，銀觸媒對於過氧化氫擁有非常好的反應效率，但也因其低熔點的特性無法承受高於92%的過氧化氫，而引來燒熔、燒結(sintering)現象造成活性物質的喪失和有效表面積的減少，燒結的效應更會伴隨著低溫反應不完全、分解室壓力震盪，甚至造成流量供給不穩定等的不利於推進的現象產生，能夠改善此問題的方法除了降低過氧化氫的濃度之外便是選用其他耐溫的過渡金屬或為其活性氧化物做為替代性觸媒，然而降低過氧化氫濃度會大幅降低其反應效率，顯然不是最佳的解決方案，在經過各國對過渡金屬觸媒活性進行一系列的檢測後，氧化錳觸媒常被篩選出來，作為過氧化氫單基推進器的分解觸媒。各國發展錳觸媒及其觸媒床設計各有其機密配方，常受管制或專利限制不易取得相關資訊，本文擬研究開發相關錳觸媒的配方與製備方法。
本論文利用金屬錳前驅液含浸γ-氧化鋁(γ- Al2O3)載體，從觸媒含浸法製程步驟上的變化，了解觸媒產物之物性變化且以分解溫度和產氣率比較檢驗各氧化錳觸媒樣本對過氧化氫之活性優劣，進而選取優化的氧化錳觸媒性能參數規劃設計1N等級推進器進行推力測試，擷取其艙壓、燃燒室溫度、質流率及推力數值，以C*effieciency、Isp等推進參數作為判定推進器性能的根據，進而以長時間與反覆測試以及脈衝測試檢驗觸媒的耐久性能、穩定性能與反應延遲特性，檢驗此觸媒能夠適用於太空任務的單基推進系統中。

Recently, hydrogen peroxide finds renewed interests and attention in space propulsion community due to the strong growing demand of non-toxic and environment-friendly “green” propellants. For monopropellant thrusters used in space propulsion applications, silver and manganese oxides are generally used as the catalyst to decompose hydrogen peroxide to generate thrust. The problem with the silver catalyst is that the melting temperature for silver is low and close to the maximum decomposition temperature of hydrogen peroxide that limits silver catalyst in very high concentration hydrogen peroxide applications. The purpose of this thesis is to re-examine the catalyst formation and fabrication process to develop the manganese oxides catalysts superior in catalytic performance and sustainable in high temperature decomposition of hydrogen peroxide for space propulsion applications.

By adjusting key parameters of distinct catalyst fabrication steps such as calcination temperatures, precursors and solvents, we examine and analyze the constituents of the different resultant manganese oxides catalysts by using different instruments of SEM、XRD、EDS. The comparison and selection of the resultant manganese oxides catalysts is based on catalytic activity test in a reactor with 50% and 70% concentration H2O2 solution and the performance of the catalyst bed made of the selected catalyst is demonstrated on a 1N grade monopropellant thruster.

The experimental results show that the active material load on γ-Al2O3 prepared by acetone solvent is greater than that on support prepared by using water as solvent,and it has superior uniformity of catalyst distribution on the support. The nominal catalyst content can be expressed as α-type Na0.07MnO2.05(PDF-270751) by XRD after regression analysis. The reactivity of the selected catalysts based on the decomposition of the hydrogen peroxide is found to decrease with increase of the calcination temperature of the catalyst for all the cases tested. The results of the thruster performance tests show that the selected manganese oxide catalysts can achieve comparable performance with the parameters of C* efficiency about 92.8%, the average atmospheric Isp 97.84sec, and ignition delay time about 300ms.

In summary, (1) the active material loads on γ-Al2O3 prepared by acetone solvent could reach 10-15% of the total catalyst, and it is greater than the prepared by using water. (2) the nominal catalyst content is α-type Na0.07MnO2.05(PDF-270751) with t stable the oxidation state of and the average diameter of the active material about 8.023nm, (3) tetravalent manganese is more active than trivalent manganese through the activity tests, (4) the outstanding performance of catalytic bed to decompose the hydrogen peroxide is performed on the monopropellant thruster. The manganese oxides really find potential applications in space propulsion system to overcome the sintering problem from the silver.

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