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姓名 黃士益(Shih-Yi Hung) 查詢紙本館藏 畢業系所 化學工程與材料工程學系 論文名稱 以稻殼灰分沈澱固著製備擔體銅觸媒 之反應性研究
(Preparation of Rice Husk Ash-Supported Copper Catalyst by Deposition-Precipitation )相關論文 檔案 [Endnote RIS 格式]
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摘要(中) 中文摘要
本研究以稻殼為起始原料，經過水洗、酸洗、熱解及碳燒等前處理方法，製成稻殼灰分，並以其為擔體，利用沈澱固著法製備成稻殼灰分擔體銅觸媒(簡稱為Cu/RHA觸媒)，同時利用感應耦合電漿質譜儀(ICP-MS)、元素分析儀(EA)、感應耦合電漿原子放射光譜儀(ICP-AES)、氮吸附法、X射線繞射儀(XRD)、熱重分析儀(TGA)、程式升溫還原(TPR)、N2O分解吸附(dissociative adsorption of nitrous oxide)及掃描式電子顯微鏡(SEM)等各項儀器與分析技術，分別對擔體及觸媒進行鑑定，並利用乙醇脫氫反應作為催化活性的測試，藉以評估稻殼灰分做為觸媒擔體的可行性，
在稻殼灰分的組成分析方面，從分析結果得知：二氧化矽的純度達99％，其晶態屬於非晶型的二氧化矽，氮吸附分析結果指出其BET比表面積約為153m2/g。而在稻殼灰分擔體銅觸媒(Cu/RHA)方面，從分析結果得知：沈澱固著乾燥後所形成的觸媒前趨物為一種類似孔雀(chrysocolla-like)的層狀矽酸銅(copper hydrosilicate)結構，而矽酸銅熱分解溫度至少要673K，且層狀矽酸銅在高溫下鍛燒會分解成高表面積的網狀結構。由氮吸附結果指出，鍛燒後的Cu/RHA觸媒，其BET比表面積隨銅金屬載量增加而增加。從TPR圖譜可看出，Cu/RHA觸媒的還原溫度隨銅金屬載量增加而降低。從N2O分解吸附結果可知，Cu/RHA觸媒的分散度隨銅金屬載量增加而降低，但銅平均粒徑隨銅金屬載量增加而變大。從XRD圖譜也可看出銅粒徑有增加的趨勢。隨著金屬載量的增加，將有助於觸媒表面活性積數目的增加，然而過高的載量，會造成銅晶粒變大，整體對乙醇的吸附能力便弱，將造成活性下降。鍛燒的條件會影響觸媒活性，最佳的鍛燒溫度為673k。最佳的還原溫度為573k，最佳的還原時間1hr。 19.8wt.% Cu/RHA觸媒在548K下進行乙醇脫氫反應，能發揮最佳的活性，但隨著反應的進行因產生積碳現象而使活性衰退，一直到130分鐘才趨於穩定。比較稻殼灰分與氧化矽膠的分析結果，稻殼灰分確實有異於氧化矽膠的擔體性質存在，不僅能負載較多的銅活性金屬，也可使負載於表面的銅金屬有較高的金屬表面積，而且分散性佳，應用於催化反應時也較不易積碳，有較佳的活性表現。摘要(英) Abstract
In this work, rice husk ash (RHA) was used as a catalyst support. RHA-supported copper catalysts (Cu/RHA) were prepared by the deposition-precipitation method. Characterization of the RHA-supported copper catalysts (Cu/RHA) indicates that the formation of the copper hydrosilicate with structural properties similar to the mineral chrysocolla. The thermal decomposition of the copper hydrosilicate starts above 673K. The specific surface area of the calcinated catalysts increases with increasing the copper loading. The dispersion of copper catalysts decreases with increasing copper loading. Furthermore, the mean size of copper crystallites increases with an increase in copper loading.
RHA supported copper catalysts was tested by the dehydrogenation of ethanol at 473-548K. The results indicate that the optimal preparations and operating conditions are 19.8wt.% in copper loading, 673K in calcination temperature, 573K in reduction temperature, 1hr in reduction time and 548K in reaction temperature.
Moreover, copper catalysts supported on RHA display higher catalytic activity than those supported on silica gel, as revealed by the test of ethanol dehydrogenation. Thus, RHA is found to be preferable over silica gel as a support.關鍵字(中) ★ 稻殼灰分
★ 擔體銅觸媒
★ 沉澱固著關鍵字(英) ★ copper catalyst
★ deposition-percipitation
★ rice husk ash論文目次 目錄
內容 頁數
中文摘要 ……………………………………..…………………… Ⅰ
英文摘要 ……………………………………..…………………… Ⅲ
目錄 ………………………………………..………………… Ⅳ
圖索引 …………………………………………..……………… Ⅶ
表索引 …………………………………………….……………. XII
第一章 緒論……………………….……………………. 1
1.1 研究背景與動機…………….….……………………… 1
1.2 研究內容與本論文的架構..…………………………… 6
第二章 文獻回顧……………………………………….. 8
2.1 稻殼的組成與性質……………………….……………. 8
2.2 稻殼灰分擔體的製備…………………….……………. 12
2.2-1 稻殼的酸洗…………………………………………... 12
2.2-2 稻殼的熱解…………………………………………... 13
2.3 沈澱固著法製備擔體銅觸媒……….…………………. 14
2.4 鍛燒與還原程序…………………….…………………. 16
2.4-1 鍛燒程序……………………………………………... 16
2.4-2 還原程序……………………………………………... 18
2.5 擔體效應…………………………….…………………. 18
2.6 銅金屬表面積的測定……………….…………………. 19
2.7 乙醇脫氫反應…………………………………………. 20
第 三章 實驗方法與裝置……………………………….. 23
3.1 稻殼灰分擔體的製備……………….…………………. 23
3.1-1 水洗程序……………………………………………... 23
3.1-2 酸洗程序……………………………………………... 23
3.1-3 熱解程序……………………………………………... 24
3.1-4 碳燒程序……………………………………………... 26
3.2 擔體銅觸媒的製備……………………………………. 29
3.2-1 觸媒製備程序………………………………………... 29
3.2-2 觸媒代號說明………………………………………... 31
3.3 稻殼灰分擔體與擔體銅觸媒的鑑定分析….……….. 31
3.3-1 感應耦合電漿質譜儀(ICP-MS)及感應耦合電漿原子放射光譜儀(ICP-AES)分析……..…………………... 32
3.3-2 元素分析(EA)………………………………………... 33
3.3-3 BET比表面積、孔隙體積及孔徑大小分佈的分析… 33
3.3-4 X-射線繞射分析(XRD)……………..………………... 34
3.3-5 熱重分析(TGA)……………………..………………... 36
3.3-6 程式升溫還原(TPR)………………..………………... 36
3.3-7 銅金屬表面積的量測…….………..………………... 39
3.3-8 掃描式電子顯微鏡(SEM)……………………….…... 41
3.4 觸媒的活性測試 乙醇脫氫反應…………………. 42
3.5 3.5-1 3.5-2 實驗流程與操作變數………………………………….稻殼灰分(RHA)的製備………………………………..稻殼灰分擔體銅觸媒………………………………….. 444444
3.6 3.6-1 3.6-2 3.6-3 數據的計算與實例…………………………………….擔體銅觸媒理論載量的定義及計算………………….銅的分散度、比金屬表面積及晶粒的定義與計算….轉化率的定義與計算…………………………………. 46464649
3.7 3.7-1 3.7-2 3.7-3 藥品、氣體及儀器設備……………………………藥品…………………………………………………….氣體……………………………………………………..儀器設備……………………………………………….. 50505252
第四章 結果與討論…………………………………….. 54
4.1 稻殼灰分組成的分析…………………………………. 54
4.2 Cu/RHA觸媒製備條件的探討……………………….. 57
4.2-1 配製濃度對銅金屬載量的影響…………….…………. 57
4.2-2 鍛燒條件的選擇……………………………………….. 60
4.3 Cu/RHA觸媒的特性分析…………………………….. 62
4.3-1 觸媒總表面積的測定結果……………………………. 62
4.3-2 銅金屬表面積的測定結果…….………………………. 64
4.3-3 X-射線繞射(XRD)的分析結果………….……………. 69
4.3-4 程式升溫還原(TPR)的分析結果……………………… 73
4.4 Cu/RHA觸媒的化性分析……………………………. 76
4.4-14.4-24.4-3 Cu/RHA觸媒的金屬載量對活性的影響…………….Cu/RHA觸媒的鍛燒溫度對活性的影響……………..Cu/RHA觸媒的還原條件對活性的影響……………. 767879
4.4-44.4-5 反應溫度對乙醇脫氫反應的影響……………………..反應時間對Cu/RHA之影響…………………………. 8383
4.4-6 稻殼灰分與商用氧化矽膠分析結果的比較………... 88
第五章 結論…………………………………………….. 96
參考文獻 …………………………………………………………. 98
圖索引
Page
Fig. 2-1 The proposed structure for chrysocolla……………..…… 17
Fig. 3-1 Schematic diagram of the apparatus for the acid leaching of rice husk……………………………….……………… 25
Fig. 3-2 Schematic diagram of the apparatus for pyrolyzed of leached rice husk…………………………….………… 27
Fig. 3-3 Apparatus for removing carbon from pyrolyzed rice husk……………………………………………………. 28
Fig. 3-4 Apparatus for catalyst calcination………..……………. 30
Fig. 3-5 Schematic diagram of temperature-programmed reduction system………...…………………………….. 38
Fig. 3-6Fig. 3-7 Schematic diagram of nitrous oxide dissociative adsorption system…..…………………………………..Schematic diagram of reaction system………………….. 4043
Fig. 3-8 Experimental flow chart for preparation of rice husk ash……………………………………………….…….. 45
Fig. 3-9 Experimental flow chart for preparation of copper- containing catalyst on rice husk ash…………………… 47
Fig.3-10Fig. 4-1 The profile of products chromatograph qualitive analysis…………………………………………………XRD spectrum of rice husk ash………………..……… 5156
Fig. 4-2 Effect of copper ion concentration on copper loading of Cu/RHA………………….……………………………. 59
Fig. 4-3Fig.4-4 Thermal gravimetric analysis (TGA) diagram of 40.3wt/% Cu/RHA catalyst precursor after drying……SEM image of various Cu/RHA catalysts after calcination at 673K (a)8.51wt.%；(b) 19.8wt.% ; (c)32.1wt.%.；(d) 40.3wt.%…………………………… 6165
Fig. 4-5 Standard XRD speactra of CuO…………………………. 70
Fig. 4-6 XRD spectra of CuO unsupported and Cu/RHA catalyst precursors with different copper ion concentration. ( precipitation time, 24h ; calcination temperature, 673K ; calcination time, 4h )(a) CuO unsupported ; (b) 8.51wt.% ; (c) 12.9wt.% ;(d) 19.8wt.% ; (e)32.1wt.%.；(f) 40.3wt.%……….…… 71
Fig. 4-7 XRD spectra of unsupported CuO and 8.51wt.% Cu/RHA catalyst precursors with different calcination temperature.(a)573K ; (b) 673K ;(c)773K(precipitation time, 24h；calcination time, 4h)………………………… 72
Fig. 4-8 TPR profiles of unsupported CuO and Cu/RHA catalysts with different copper loading.(a) unsupported CuO; (b) 8.51wt.% ; (c) 12.9wt.% ; (d) 19.8wt.% ; (e) 32.1wt.%.；(f)40.3 wt.% ( ramp rate, 10K/min ; precipitation time, 24h ; calcination temperature, 673K ; calcination time, 4h )………………. 74
Fig.4-9 TPR profiles of CuO unsupported and 8.51wt.% Cu/RHA catalyst precursors with different calcination temperature. ( precipitation time, 24h ; calcination time, 4h )(a)573K ; (b) 673K ; (c) 773K………………………….. 75
Fig4-10 Effect of copper loading on ethanol conversion for ethanol dehydrogenation over Cu/RHA catalysts (calcination temperature, 673K；calcination time, 4hr；reaction tempure, 548K；reaction time, 40 min.)………. 77
Fig.4-11 Effect of calcination temperature on ethanol conversion for ethanol dehydrogenation over 8.51wt.% Cu/RHA catalyst (calcination time,4 hr；reaction tempure,548K；reaction time,40 min.)…………………………………… 80
Fig.4-12 Effect of reduction temperature on ethanol conversion for ethanol dehydrogenation over 19.8wt.%Cu/RHA catalysts(calcination temperature ,673K；calcinations time 4 hr；reaction tempure,548K；reaction time,40 min.). 81
Fig. 4-13 Effect of reduction time on ethanol conversion for ethanol dehydrogenation over 19.8wt.% Cu/RHA catalysts(calcination temperature ,673K；calcinations time 4 hr；reaction tempure,548K；reaction time,40 min.) 83
Fig. 4-14 The profile of products chromatograph qualitative analysis. (copper loading 40.3wt.%；reaction temperature 573K)……………………………………………………. 84
Fig. 4-15 Effect of reaction temrerature on ethanol conversion for ethanol dehydrogenation over 19.8wt.% Cu/RHA catalysts (calcination temperature, 673K；calcination time, 4 hr；reduction tempure,578K；reaction time, 40 min.)……………………………………………………… 85
Fig. 4-16 Effect of reaction time on ethanol conversion for ethanol dehydrogenation over 19.8wt.% Cu/RHA catalysts (calcination temperature,673K；calcination time 4 hr；reaction tempure,548K)…………………………………. 87
Fig. 4-17 XRD spectrum of rice husk ash and silica gel…………… 90
Fig. 4-18 Comparison of on ethanol conversion for ethanol dehydrogenation over Cu/RHA and Cu/SiO2 catalysts(a)Cu/RHA (b)Cu/SiO2 (reaction temperature,548K)……. 95
表索引
Page
Table 1-1 The utilization of rice husk……………………...…. 4
Table 2-1 Organic constituent of rice husk. …………………... 9
Table 2-2 Chemical analysis of raw rice husk……………… 10
Table 2-3 Average composition of rice husk ash……………… 11
Table 4-1 The ICP-MS analysis and element analysis of rice husk ash…………………………………………… 55
Table 4-2 The ICP-AES analysis of Cu/RHA catalysts with different prepared condition……………………… 58
Table 4-3 Nitrogen adsorption analysis of Cu/RHA catalysts with different copper ion concentration……..……... 63
Table 4-4 The dissociative adsorption of nitrous oxide analysis of Cu/RHA catalysts with different copper ion concentration. ( precipitation time, 24h ; calcination temperature, 673K ; calcination time, 4h ; reduction temperature, 673K )……………………………...… 66
Table 4-5 The dissociative adsorption of nitrous oxide analysis of 8.51wt% Cu/RHA catalysts with different calcination temperature. ( precipitation time, 24h ; calcination time, 4h ; reduction temperature, 673K )….…………………………………………… 68
Table 4-6 Comparison of physical properties of rice husk ash and silica gel……………………………………….. 89
Table 4-7 Comparison of nitrogen adsorption analysis of Cu/RHA and Cu/SiO2……………………………. 92
Table 4-8 Comparison of nitrous oxide analysis of Cu/RHA and Cu/SiO2 catalysts……………………………. 93參考文獻 參考文獻
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