以稻殼灰分沈澱固著製備擔體銅觸媒之特性研究

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謝銘仲(Ming-Chung Hsieh) 查詢紙本館藏

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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特性研究
(Characterization of rice husk ash-supported copper catalysts prepared by deposition-precipitation method)

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摘要(中)

本研究以稻殼為原料，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)，同時輔以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)、掃描式電子顯微鏡(SEM)及穿透式電子顯微鏡(TEM)等各項儀器與分析技術，分別對擔體及觸媒進行特性分析，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113m2/g，為一非多孔性物質，孔洞形狀則為圓形，利用電子顯微鏡觀察其表面結構及粒子大小，可知其表面相當平滑、粒子大小約為100nm。
而在稻殼灰分擔體銅觸媒(Cu/RHA)方面，從分析結果得知：當恆溫沈澱時間超過12小時，有最大的銅負載量。沈澱固著乾燥後所形成的觸媒前趨物為一種類似孔雀石(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。由氮吸附結果指出，不論是鍛燒後或還原後的Cu/RHA觸媒，其BET比表面積隨銅金屬載量增加而增加，而且高載量Cu/RHA觸媒的孔洞形狀呈狹縫型。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。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，未來應用於催化反應時，應有較佳的活性表現。

摘要(英)

In this work, the rice husk ash (RHA) was used as a catalyst support. The RHA-supported copper catalysts (Cu/RHA) were prepared by the deposition-precipitation technique. The RHA and Cu/RHA catalysts were characterized by inductively coupled plasma-mass spectrometer (ICP- MS), element analysis (EA), inductively coupled plasma-atomic emission spectrometer (ICP-AES), nitrogen adsorption method, X-ray diffraction (XRD), thermogravimetric analyzer (TGA), temperature-programmed reduction (TPR), dissociative adsorption of nitrous oxide, scanning electron microscopy (SEM), and transmission electron microscopy (TEM).
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. Increasing the copper loading, both the calcined and reduced catalysts, causes the specific surface area to rise, and the pore shape of catalysts is changed from “spherical” to “slit-like”. The dispersion of copper decreases with increasing copper loading. The copper surface area increases with copper loading up to 31.0 wt.% and then decreases with further increase in copper loading. Furthermore, the mean size of copper crystallites increases with an increase in copper loading.
Moreover, RHA is found to be preferable over silica gel as a support as revealed by the TPR and dissociative adsorption of N2O.

關鍵字(中)

★ 沈澱固著法
★ 擔體銅觸媒
★ 稻殼灰分
★ 特性

關鍵字(英)

★ Characterization
★ Deposition-Precipitation
★ Supported copper catalyst
★ Rice husk ash

論文目次

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..…………………………… 4
第二章文獻回顧………………………………………........ 7
2.1 稻殼的組成與性質……………………….……………. 7
2.2 稻殼灰分擔體的製備…………………….……………. 11
2.2-1 稻殼的酸洗…………………………………………... 11
2.2-2 稻殼的熱解…………………………………………... 12
2.3 沈澱固著法製備擔體銅觸媒……….…………………. 13
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……………………………………………... 17
2.5 擔體效應…………………………….…………………. 17
2.6 銅金屬表面積的測定……………….…………………. 18
第三章實驗方法與裝置……………………………….. 21
3.1 稻殼灰分擔體的製備……………….…………………. 21
3.1-1 水洗程序……………………………………………... 21
3.1-2 酸洗程序……………………………………………... 21
3.1-3 熱解程序……………………………………………... 23
3.1-4 碳燒程序……………………………………………... 25
3.2 擔體銅觸媒的製備…………………………………….. 27
3.2-1 觸媒製備程序………………………………………... 27
3.2-2 觸媒代號說明………………………………………... 29
3.3 稻殼灰分擔體與擔體銅觸媒的鑑定分析….………... 30
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……..…………………......... 31
3.3-2 元素分析(EA)………………………………………... 31
3.3-3 BET比表面積、孔隙體積及孔徑大小分佈的分析… 32
3.3-4 X-射線繞射分析(XRD)……………..……………….. 34
3.3-5 熱重分析(TGA)……………………..……………….. 35
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
3.3-9 穿透式電子顯微鏡(TEM)..…………..…………….. 42
3.4 實驗流程與操作變數………………………………….. 43
3.5 數據的計算與實例…………………………………….. 46
3.6 藥品、氣體及儀器設備…………………………….............49
第四章結果與討論……………………………………........ 52
4.1 稻殼灰分組成的分析…………………………………... 52
4.2 Cu/RHA觸媒製備條件的探討……………………….... 54
4.2-1 配製濃度對銅金屬載量的影響…………….………… 54
4.2-2 恆溫沈澱時間對銅金屬載量的影響……….………… 58
4.2-3 鍛燒條件的選擇………………………………………. 60
4.3 Cu/RHA觸媒的特性分析…………………………….... 63
4.3-1 觸媒總表面積的測定結果……………………………. 63
4.3-2 銅金屬表面積的測定結果…….……………………… 74
4.3-3 X-射線繞射(XRD)的分析結果………….……………. 82
4.3-4 程式升溫還原(TPR)的分析結果……………………… 91
4.3-5 掃描式電子顯微鏡(SEM)的分析結果……….………. 97
4.3-6 穿透式電子顯微鏡(TEM)的分析結果……………….. 99
4.4 稻殼灰分與商用氧化矽膠分析結果的比較……….... 102
第五章結論……………………………………………........ 112
參考文獻 ………………………………………..………………......... 114
附錄A 實驗數據……………………….………………....... 122
附錄B XRD標準圖譜……………….…………………........ 124

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指導教授

張奉文(Feg-Wen Chang)

審核日期

2002-6-28

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