臺灣博碩士論文加值系統

氫氣為一種理想潔淨的能源載體，使用生質乙醇製氫，可以使二氧化碳成為一封閉的碳循環，而達到近乎零碳排放的目標。本實驗室先前研究顯示利用模板法合成之銅鎳觸媒中的CuNi-NiO界面有利乙醇蒸氣重組反應，可在溫和條件下催化乙醇重組獲得高氫氣產率，為了提高CuNi- NiO界面在H2中的穩定性，並開發簡易實用的觸媒製備方法。本研究以不同比例La、Gd摻雜NiO作為載體製作觸媒，期望藉由提升NiO還原溫度以維持活性界面，研究中並改變不同前處理條件進行比較討論。
研究結果顯示摻雜15%La觸媒於P-2(250℃, 30min)半還原條件下可使觸媒還原程度接近50%，且CuNi合金和NiO晶粒較小，能產生較穩定且活性較好的CuNi-NiO界面，在反應溫度350℃時，在本研究的操作下可使EtOH幾乎完全轉化，含碳產物含有約20％CH4、15％CO、60％的CO2，H2的產率為3.8。比較不同摻雜金屬與其含量，摻雜La觸媒有優於摻雜Gd觸媒之反應速率，提高摻雜金屬含量會使反應活化能提高，對反應乙醇蒸氣重組有較好的改善。
Cu/La15-NiO-P2觸媒在325℃持溫10小時可以保持穩定反應活性，得知反應後觸媒仍具有NiO結構，顯示可以穩定維持ESR反應活性，在10小時內仍可產生穩定的H2；說明Cu/La15-NiO觸媒中，摻雜金屬的NiO可以促使CuNi-NiO活性界面在較溫和反應條件下穩定存在。

關鍵字: 銅鎳觸媒、前處理、蒸氣重組、金屬氧化物界面

Hydrogen is an ideal clean carrier. Zero carbon emissions can be achieved by using, hydrogen from the reforming of bio-ethanol. In our previous study CuNi-NiO interface in a (Cu-NiO) catalyst prepared by hard-template method can have good activity in ethanol steam reforming reaction(ESR), obtaining high hydrogen yield at mildle conditions. This study intends to improve the stability of CuNi-NiO interface and to prepare workable catalyst preparation method for industal application. In this study dope La and Gd in NiO as support for Cu, expecting the acticity interface can be stabilized by an increase in the NiO reduction temperature.
The results show that Cu/La15-NiO after P-2 pretreatment (250 ℃, 30min) have a degree of reduction of around 50% and good ESR activity. The CuNi alloy and NiO particle size are smaller than other catalysts, which can result in more CuNi-NiO interface. At 350℃, EtOH is nearly completely converted with C-products including 20% CH4, 15% CO and 60% CO2 and a H2 yield of 3.8. Comparing with different type and amount of dopant, the La-doped catalysts have better reaction performance than the Gd-doped catalysts.
The stability test of Cu/La15-NiO-P2 catalyst at 325℃ for 10 hours, indicate stable ESR activity the same H2 yield, the spent catalyst still contain NiO structure, indicating that the metal–doped Cu/La15-NiO catalyst can maintain stable CuNi-NiO interface under the ESR condition.

Keywords: Copper-nickel catalysts, pretreatment, steam reforming, metal oxide interface.

摘要 I
Abstract II
目錄 III
圖目錄 V
表目錄 VI
第一章 緒論 1
1.1前言 1
1.2文獻回顧 2
1.2.1 乙醇製氫反應 2
1.2.2 銅鎳觸媒應用於乙醇蒸氣重組反應 3
1.2.3利用半還原銅鎳觸媒進行蒸氣重組反應 5
1.2.4 氧化鎳結構摻雜金屬對其還原峰影響 6
1.3 研究目的 10
第二章 研究設備與方法 11
2.1觸媒命名 11
2.2 研究架構及方法 12
2.3藥品及儀器設備 13
2.3.1藥品部分 13
2.3.2氣體部分 13
2.3.3儀器部分 14
2.4觸媒製備 14
2.4.1以共沉澱法製備 MX-NiO (M=La, Gd) 觸媒 14
2.4.2以初濕含浸法製備10%Cu/MX-NiO (M=La, Gd) 觸媒 15
2.4.3 SBA-15中孔洞氧化矽基材之製備 15
2.4.4以SBA-15為模板製備(NiO)sc觸媒 15
2.4.5以初濕含浸法製備Cu/(NiO)sc觸媒 16
2.5觸媒特性分析 17
2.5.1X光粉末繞射儀(XRD) 17
2.5.2程序升溫還原系統(TPR) 17
2.5.3比表面積與孔隙測定儀(BET) 18
2.5.4熱重分析儀(TGA) 18
2.5.5NSRRC EXAFS 18
2.5.6乙醇蒸氣重組反應(ESR) 18
第三章 結果與討論 20
3.1Cu/(NiO)sc觸媒和Cu/NiO觸媒之特性分析與ESR反應 20
3.1.1Cu/(NiO)sc與Cu/NiO觸媒特性分析 20
3.1.2Cu/NiO觸媒與(Cu-NiO)sc觸媒之ESR反應 26
3.2摻雜過渡金屬修飾氧化鎳載體效果及ESR反應 32
3.2.1 MX-NiO(M=La, Gd)觸媒特性分析 32
3.2.2 不同前處理理條件對於觸媒組成及反應之影響 40
3.2.3 動力學分析 68
3.3.綜合討論 74
3.3.1P-2前處理觸媒反應前後結構對ESR反應影響 74
3.3.2不同溫度下產物選擇率趨勢分析 79
3.3.3Cu/La15-NiO-P2穩定性測試 82
第四章 結論 85
Future Work 87
參考文獻 88
附錄 92
附錄A-ESR反應機制 92
附錄B-N2O吸附計算 93
附錄C-Origin分峰計算方式 94
附錄D-EXFAS分析 95
附錄E 102
I. Cu/M15-NiO-P2 TGA分析 102
II. 其他金屬修飾NiO載體 104
III. 比較含浸與共沉澱Cu於La15-NiO之差別 108
IV. 以Cu/La15-NiO之觸媒加入載體(MgO, ZrO2, Al2O3)對ESR影響 113

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