臺灣博碩士論文加值系統

乙醇可以用作生產清潔能源的載體，在產生氫氣具有巨大的潛力，減少使用化石燃料產生的二氧化碳排放。乙醇氧化蒸汽重組氣（OSRE）是產生氫氣方法之一，主要是將乙醇的蒸汽重組反應（SRE）和乙醇的部分氧化（POE）整合在一起。我們的研究中，主要以乙醇氧化蒸汽重組氣（OSRE）產生氫氣為主。首先，研究觸媒材料金屬Ni和NiO對載體材料及對產生氫氣效能的影響。我們使用了Al2O3、ZrO2不同載體材料及實驗室製造載體材料La2Zr2O7（LZO），且將金屬Ni和NiO含浸在載體上作為活性觸媒使用。我們藉由國家同步輻射研究中心的X光射線:粉末X光繞射實驗（PXRD）和X光吸收光譜（XAS）進行研究、鑑定製備的觸媒材料。在Ni/LZO和NiO/LZO的還原和氧化環境下進行XAS-XRD實驗，發現Ni的氧化價態是影響反應催化活性的重要因素之一。在NiO/LZO觸媒在乙醇自熱重整反應（ATRE）反應，在長時間110個小時的反應催化活性，其平均乙醇轉化率和氫氣產率分別為99（1）％和56（1）％。在NiO和LZO之間的觸媒-載體相互作用力抑制了金屬Ni的聚集和碳沉積生成，相較於Ni/LZO催化劑相比，NiO/LZO表現出更好的長時間的穩定性。其次，使用同步加速器XRD和XAS研究固溶體材料，La2Ce2-xNixO7-δ（x = 0-0.45）和AxLa2-xCe1.8Ru0.2O7-δ（A = Li+，Mg2+和Ca2+）燒綠石結構材料。經由Rietveld refinement和臨場XANES對材料La2Ce2-xNixO7-δ（x = 0-0.45）進行原子及電子結構鑑定。發現純燒綠石結構的觸媒材料具有均勻分散的Ni2+活性金屬，相較在結構外含有少量NiO的觸媒具有更佳的穩定性。本研究發現主要結構分解和少量NiO團聚，是造成OSRE反應中的焦炭生成，而失去反應活性的原因。在對於Ru取代的燒綠石結構研究，AxLa2-xCe1.8Ru0.2O7-δ（A = Li+，Mg2+和Ca2+）的結構鑑定指出Ru離子具有高氧化價態存在，可以歸因於Ce4+和Ce3+之間的電荷重新分佈而且Ru離子可藉由摻入的Li+，Mg2+和Ca2+離子電荷補償，達到結構中的電荷平衡。在燒綠石結構中Mg2+和Ca2+的取代，主要藉由氧空缺生成達成電荷價態平衡。實驗結果發現，高價態的活性金屬Ru離子和本實驗室製造的LZO載體材料，促進了乙醇的OSR和ATR的催化反應活性和穩定性。最後，在研究層狀鈣鈦礦氧化物La2Ti2-xRuxO7±δ（LTRO）中金屬Ru取代的影響。在釕和氧的吸收光譜發現釕與氧之間的作用力隨著摻雜而增加。經由粉末繞射和Rietveld refinement實驗，發現在還原過程中Ru離子的還原，主要釋放位於平板中心和邊緣位置的Ru離子的氧原子1、6、12位置。在還原過程中，第一步還原指出，平板中心高氧化態的Ru離子可以有效的吸附乙醇，以進行初始脫氫反應，生成乙醛和氫氣。然後，通過第二步還原過程，平板中心和邊緣位置的Ru離子則以進行碳鍵裂解和氫氣的產生為主。

Hydrogen production from ethanol has a great potential to be utilized as a clean energy carrier for reducing CO2 emission from fossil fuel consumption. Oxidative steam reforming of ethanol (OSRE) is one of hydrogen production processes that integrates steam reforming reaction of ethanol (SRE) and partial oxidation of ethanol (POE) to minimize the energy input. In this study, we studied catalytic ethanol of conversion on OSRE with varies catalysts and supporting materials. The first part contains the investigations on the Ni and NiO catalysts. The activity of metallic Ni and NiO supported on Al2O3, ZrO2 and lab-made supporting materials La2Zr2O7 (LZO) were studied. The as-prepared catalyst was characterized by powder X-ray diffraction (PXRD) and X-ray absorption spectroscopy (XAS) using X-ray source in National Synchrotron Radiation Research Center (Taiwan). The combined XAS-XRD experiments under reductive and oxidative conditions of Ni/LZO and NiO/LZO indicated that the oxidation states of nickel was an important factor to affect catalytic reactivity. The time on stream test of autothermal reforming of ethanol reaction (ATRE) on NiO/LZO catalyst exhibited stable catalytic performance for 110 hours with average ethanol conversion rate and hydrogen yield of 99(1)% and 56(1)%, respectively. The strong catalyst-support interaction between NiO and LZO suppressed the aggregation of metallic Ni and carbon deposition. The metal oxide catalyst NiO/LZO exhibited better long-term stability compared to Ni/LZO catalyst reduced particle aggregation and carbon deposition. Secondly, pyrochlore structures of La2Ce2-xNixO7-δ (x = 0-0.45) and AxLa2-xCe1.8Ru0.2O7-δ (A = Li+, Mg2+, and Ca2+) were studied by using synchrotron XRD and XAS. The materials La2Ce2-xNixO7-δ (x = 0-0.45) were characterized by Rietveld Refinement and in-situ XANES to realize the electronic structure. A catalyst with a pure pyrochlore phase contained evenly distributed nickel atoms, and was more stable than a catalyst containing a small amount of NiO. For the Ru-substituted pyrochlore structure, the series of AxLa2-xCe1.8Ru0.2O7-δ (A = Li+, Mg2+, and Ca2+) catalysts contain high oxidation states of Ru ions and the charge redistribution between Ce and Ru ions to compensate the incorporated Li+, Mg2+ and Ca2+ ions. The substituted of Mg2+ and Ca2+ in the pyrochlore structure created oxygen vacancies and high oxidation states of Ru ions, and the catalysts supported on LZO show high performance and stability in OSR and ATR of ethanol. Finally, the effect of the metal substitution in the layered perovskite oxides La2Ti2-xRuxO7±δ (LTRO) were investigated to realize the effect of site preference on active metal Ru ions to OSRE activity. The relationship between structure and activity were revealed by using synchrotron XRD and XAS and the oxidation-reduction procedure. With the in-situ diffraction experiment and Rietveld refinements, the distribution of Ru ions located in center and edge positions of slab, and oxygen atoms in the O1, O6, and O12 sites were released because of the reduction from Run+ ions during the reduction process. The high oxidation state Run+ ions could effectively adsorb ethanol to initialize dehydrogenation reaction to form acetaldehyde and subsequent hydrogen production. Then, the second reduction step was active for decomposition of carbon species and hydrogen production.

摘 要....................................i
Abstract.......................................iii
Acknowledgements...............................v
Contents.......................................vi
List of Tables.................................vii
List of Figures................................viii
Chapter 1 Introduction.........................1
1.1. Ethanol conversion process................1
1.2. Mechanism of the oxidative steam reforming of ethanol........................................5
1.3. Literature review.........................8
1.4. Challenges and strategies for oxidative steam reforming of ethanol...........................20
1.5. Motivation................................28
Chapter 2 Experimental.........................33
2.1 Materials..................................33
2.2 Apparatus..................................34
2.3 Synthesis..................................35
2.4. Catalytic activity........................36
2.5. Characterization..........................38
2.6. Calculation of selectivity in the OSRE reaction ...............................................46
Chapter 3 Results and Discussion...............49
3.1 Nickel and nickel oxide based catalyst.....49
3.2 Pyrochlore metal oxide catalysts...........107
3.3 Layer-perovskite structure La2Ti2-xRuxO7±δ (x = 0.0-0.4)...........................................173
Chapter 4 Conclusion and perspectives..........197
4.1 Conclusion.................................197
4.2 Perspectives...............................199
Reference......................................211

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