臺灣博碩士論文加值系統

本研究利用過氧化氫和甲醇混合應用於甲醇氧化蒸氣重組(H2O2-OSRM)反應，以液態進樣於甲醇重組器，能有助於燃料電池的整合。在H2O2-OSRM的測試當中，過氧化氫會在150℃能完全分解成水跟氧氣，當甲醇和過氧化氫體積比為4:1(O2/MeOH =0.089、H2O/MOH=0.514)，在250℃的環境下，CuPd2/Ce10Zn (30 wt% Cu, 2 wt% Pd, 10 wt% Ce and 58wt% Zn)和CuPd2/Ce20Zn (30 wt% Cu, 2 wt% Pd, 20 wt% Ce and 48wt% Zn)兩種觸媒甲醇轉換率將近80%，氫氣產率2.5，CO選擇率也只有3%，而且當觸媒中鈰的含量提高時，更可以有效的降低CO的產生；隨著甲醇和過氧化氫體積比提升至3:1(O2/MeOH =0.119、H2O/MOH=0.685)，因O2/MeOH的提升，能增進觸媒在低溫的甲醇轉換率。將觸媒經過氫氣預還原後應用至H2O2-OSRM系統中，發現可以有效改善觸媒在低溫的反應性。和傳統的SRM (H2O/MOH=0.514和H2O/MOH=0.685)做個比較，H2O2-OSRM的系統中，整體的甲醇轉換率有明顯的提升(~30%CMeOH)且在250℃的產氫量比SRM高了1.7倍。CuPd2/Ce10Zn 和CuPd2/Ce20Zn兩種觸媒在傳統的OSRM (O2/MeOH =0.3、H2O/MOH=0.514)反應中擁有很好的反應性，在250℃的環境下，甲醇轉換率就接近90%而氫氣產率接近2.5，且在低溫150℃時，甲醇轉換率也可以維持60%，整體的CO選擇率只有0-4%。由於H2O2-OSRM系統中的氧氣含量限制於過氧化氫的濃度，使得反應性無法更進一步的提升。
　　此外，為瞭解觸媒的鈰含量與降低CO之關聯，氧氣程溫脱附(O2-TPD)、CO程溫還原(CO-TPR)以及即時偵測IR光譜儀被利用來探討鈰的氧空缺對於反應性以及CO氧化的影響。結果顯示，和CuZn (30 wt% Cu and 70 wt% Zn)觸媒比較，CuPd2/Ce20Zn可以增加約10倍的氧氣以及CO的吸附量，同時能促進CO在更低的溫度下(90℃)就進行氧化反應。

This study develops a hydrogen production process from oxidative steam reforming of methanol using hydrogen peroxide as the oxidant (H2O2-OSRM). The liquid phase of H2O2 with methanol will facilitate the design and assembly of fuel cells. In the H2O2-OSRM system test, H2O2 could decompose completely at 150℃. For the catalytic activity of the catalysts in H2O2-OSRM reaction with MeOH:H2O2 volume ratio of 4:1(O2/MeOH =0.089, H2O/MOH=0.514), both CuPd2/Ce10Zn (30 wt% Cu, 2 wt% Pd, 10 wt% Ce and 58wt% Zn) and CuPd2/Ce20Zn (30 wt% Cu, 2 wt% Pd, 20 wt% Ce and 48wt% Zn) catalysts showed ~80% of CMeOH, ~2.4 of YH2, and only 3% of SCO at 250℃. With increasing the addition of Ce, the SCO can be reduced, even to 0%. In MeOH:H2O2 volume ratio of 3:1 (O2/MeOH =0.119, H2O/MOH=0.685), which can provide more oxygen to enhance catalytic activity of catalysts at low temperature. When catalysts were pre-reduced before reaction, it not only improve catalytic activity but also decrease SCO in H2O2-OSRM system .On the whole, compared with H2O2-OSRM and SRM at the same ratio of H2O/MeOH, H2O2-OSRM system can provide more hydrogen than SRM reaction. It approximately provided 1.7 times of hydrogen production at 250℃. The catalytic activity of CuPd2/Ce10Zn and CuPd2/Ce20Zn catalysts through OSRM reaction (O2/MeOH=0.3H2O/MeOH=0.514) showed good performance. CuPd2/Ce10Zn and CuPd2/Ce20Zn catalysts performed ~90% of CMeOH, ~ 2.5 of YH2 at 250℃, and the Sco was kept 0~4% at whole reaction. Since the oxygen content was limited by the concentration of hydrogen peroxide (~50%), the reactivity in H2O2-OSRM system cannot further be enhanced.
　　To more realize the effect of Ce promoter and abatement of CO, O2-TPD, CO-TPR and in-situ DRIFT were investigated to explore the relation between Ce promoter and O2 and CO chemisorption. It obviously shows that more O2 and CO were adsorbed on catalyst with Ce. CuPd2/Ce20Zn catalyst has 10 times intensity of CO chemisorption than CuZn (30 wt% Cu and 70 wt% Zn) catalyst. The presence of CeO2 with oxygen vacancies enhanced the affinity to adsorb oxygen atoms of reactants, as well as even can catalyze CO oxidation at low temperature (90℃).

Abstract I
摘要 II
誌謝 III
Category IV
List of figures VII
List of table XI
Chapter 1. Motivation and approaches 1
Chapter 2. Background and Introduction 3
2-1 Use of the energy 3
2-2 Fuel cells 4
2-3 Proton exchange membrane fuel cells (PEMFCs) 10
2-4 Production of hydrogen from methanol 14
2-5 Paper review of production hydrogen from methanol reforming 18
2-5-1 Cu based catalyst 18
2-5-2 Promoter of Pd 19
2-5-3 Promoter of Ce 21
Chapter 3. Experimental section 22
3-1 Chemicals and solutions 22
3-2 Catalysts preparation method 23
3-2-1 Cu/ZnO (Cu/Zn) (30 wt% Cu and 70 wt% Zn) 23
3-2-2 CuPd/ZnO (CuPd2/Zn) (30 wt% Cu, 2 wt% Pd and 68 wt% Zn) 24
3-2-3 CuPd/CeZnO (CuPd2/CexZn) (30 wt% Cu, 2 wt% Pd, 10-68 wt% Ce and 58-0 wt% Zn) 25
3-3 Inductively coupled plasma-mass spectrometry (ICP-Mass) 27
3-4 Vacuum system and nitrogen physical adsorption 28
3-5 Transmission electron microscopy (TEM) 31
3-6 Powder X-ray diffractometer (XRD) 32
3-7 Temperature programmed reduction (TPR) 33
3-8 N2O Chemisorption 35
3-9 Oxygen temperature programmed desorption (O2-TPD) 36
3-10 In-situ diffuse reflectance infrared fourier transform spectroscopy (in-situ DRIFTS) 38
3-11 Catalytic activity 39
Chapter 4. Results and discussion 42
4-1 Characterization of catalysts 42
4-1-1 Transmission electron microscopy 42
4-1-2 Hydrogen temperature programmed reduction 45
4-1-3 X-ray powder diffraction of the catalysts 48
4-2 Catalytic activity 51
4-2-1 catalytic activity of OSRM 51
4-2-2 catalytic activity of SRM 54
4-2-4 catalytic activity of H2O2-OSRM 58
4-2-3 H2O2-OSRM reaction over reduced catalysts 64
4-3 The mechanism of CO oxidation on Ce with oxygen vacancies 67
4-3-1 In-situ DRIFT 67
4-3-2 Temperature-programmed desorption of O2 70
4-3-3 temperature-programmed reduction of CO 72
Conclusion 76
Reference 77

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