臺灣博碩士論文加值系統

以超音波(240 W)輔助共沉澱氧化法製備鎳鑭複合氧化物觸媒，並分別煅燒300、 500和700 ℃ 兩小時。並以XRD(X-ray Diffraction)、TPR(Temperature - Programmed Reduction) 、TG、BET及TEM(Transmission Electron Microscope)鑑定觸媒特性結構。進一步探討反應溫度(300-450℃)對乙醇蒸氣重組(SRE)反應活性及產物分佈的影響。經特性鑑定結果指出鎳鑭複合氧化物觸媒經超音波輔助(U-LaNiOx)易生成管狀結構，不經超音波輔助(LaNiOx)主要生成棒狀結構。經高溫煅燒後兩種觸媒都會形成鑭酸鎳(LaNiO3)結構。經SRE(Steam Reforming Ethanol)反應活性比較。結果指出U-LaNiOx觸媒在325 ℃之乙醇轉化趨近100%，而LaNiOx觸媒之反應溫度(TR)則需達425 ℃才能完全轉化，比較氫氣產率(YH2)，U-LaNiOx觸媒在350 ℃趨近於5。LaNiOx觸媒在350 ℃只有0.36。結果指出超音波易使鎳鑭前驅物均勻分散，使得鎳鑭形成交互作用力，氧化鑭會均勻分布在鎳上，有效增加反應活性及抗積碳能力，未經超音波使的前驅物分散不夠均勻，鑭鎳交互堆積，影響活性。且鑭並未均勻分布在鎳上，無法有效去除積碳。

A nickel-lanthanum composite oxide, U-LaNiOx, with 1:1 molar ratio was prepared by the co-precipitation-oxidation method (PO) and assisted with ultrasonic irradiation (240 W). The as-prepared sample was further calcined at 300, 500 and 700 ℃ for 2 h (assigned as U-C300, U-C500 and U-C700, respectively). All samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), BET and temperature programmed reduction (TPR). Catalytic activities toward the steam reforming of ethanol (SRE) were tested in the temperature (300-450℃) in a self-designed fixed-bed reactor.The results of Characterization test confirmed that the U-LaNiOx has a nanotube structure and LaNiOx has a nanorods structure, We believe that formation of nanotubes can be attributed to the assisted with ultrasonic irradiation. Both as-prepared sample was calcined at 700 ℃ for 2 h that became perovskite structure (LaNiOx).This study focused on the comparison of activated as-prepared sample (U-LaNiOx) with the non-assisted with ultrasonic irradiation (240 W)as-prepared sample (LaNiOx). The results indicated that the ethanol conversion approached complete around 325 ℃ for U-LaNiOx sample while required 425 ℃ for LaNiOx sample to complete conversion. The yield of hydrogen (YH2) arrived 5.0 around 350 ℃ for U-LaNiOx sample.U-LaNiOx catalyst compared with LaNiOx catalyst, U-LaNiOx catalyst was highly active and stable for steam reforming of ethanol. The improvement was attributed to the effective highly dispersed LaOx particles through the strong interaction between LaOx and NiOx.

誌謝 ii
摘要 iii
ABSTRACT iv
目錄 v
表目錄 vii
圖目錄 viii
1. 緒論 1
1.1 前言 1
1.2 氫氣的生產 1
1.3 乙醇蒸氣重組製氫文獻回顧 4
1.4 超音波輔助製備文獻回顧 6
1.5 研究目的與方向 7
2. 實驗 8
2.1 藥品 8
2.2 觸媒製備 8
2.3 實驗儀器 12
2.3.1 X光粉末繞射(XRD, X-ray Powder Diffraction) 12
2.3.2 熱分析(TGA) 13
2.3.3 傅立葉轉換紅外線光譜儀(FT-IR) 13
2.3.4 程溫還原反應(TPR, Temperature Programmed Reduction) 13
2.3.5 穿透式電子顯微鏡(TEM, Transmission Electron Microscope) 16
2.3.6 表面積及孔徑量測(BET) 16
2.4 觸媒的活性測試 17
2.4.1 活性測試裝置 17
2.4.2 活性測試數據計算 21
3. 結果與討論 22
3.1 U-LaNiOx系列觸媒 22
3.1.1 觸媒特性鑑定 22
3.1.2 SRE活性測試 28
3.1.3 SRE壽期測試 36
3.1.4 U-LaNiOx系列觸媒SRE反應後之特性鑑定 37
3.1.5 U-LaNiOx觸媒進行SRE反應之機制 40
3.2 LaNiOx系列觸媒 42
3.2.1 觸媒特性鑑定 42
3.2.2 SRE活性測試 47
3.2.3 SRE反應後觸媒特性鑑定 53
3.2.4 LaNiOx觸媒進行SRE反應之機制 57
4. 結論 59
參考文獻 60
自傳 66

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