Currently among the heterogeneous catalysts used in Friedel-Crafts acylation reactions, the heteropoly acids supported by zeolite or some highly stabe metal oxides are often used. But current methods of preparing supported heteropoly acid catalysts are rather complicated and time-consuming; that is why the supported heteropoly acid catalysts have not been widely used in the industry.
In this study, we use the Dry Gel Conversion (DGC) technique combined with the Steam Assisted Conversion (SAC) technique to prepare a series of HPW/SiO2 catalysts by changing preparation parameters. By using this method, we found that the preparation procedures can be simplified significantly. The HPW/SiO2 catalysts were characterized by XRD, TEM, and FT-IR their activities were tested through the acylation of anisole and veratrole.
The XRD patterns show that the catalysts are amorphous, and the amount of supported catalyst can be reduced by rising SAC temperature and increasing SAC time. The TEM pictures indicate that the catalysts are covered by supports. By means of pyridine adsorption and FT-IR, we realize that there is more Bronsted acid than Lewis acid.
By comparing the conversions of the acylation of anisole and the acylation of veratrole with different catalysts, the optimal catalyst and reaction condition can be found.

中文摘要 i
英文摘要 ii
誌謝 iii
目錄 iv
表目錄 vi
圖目錄 vii
第一章 緒論 1
1.1 前言 1
1.2 研究目的 2
第二章 理論基礎 3
2.1 芳香族之佛瑞德－克萊福特醯化反應 3
2.2 均相觸媒與非均相觸媒 7
2.2.1 均相觸媒 9
2.2.2 非均相觸媒 11
2.3 固體酸觸媒 14
2.4 異聚酸 16
2.5 觸媒製備方法 19
2.6 文獻論述 25
第三章 實驗方法 30
3.1異聚酸載體觸媒 30
3.1.1 藥品 30
3.1.2 儀器設備 30
3.1.3 實驗方法 31
3.2茴香醚之醯化反應 34
3.2.1 藥品 34
3.2.2 儀器 34
3.2.3 實驗方法 34
3.3藜蘆醚之醯化反應 36
3.3.1 藥品 36
3.3.2 儀器 36
3.1.3 實驗方法 36
第四章 結果與討論 38
4.1 異聚酸載體觸媒分析 38
4.1.1 XRD繞射分析 38
4.1.2 傅立葉紅外光譜 43
4.1.2.1 觸媒特徵分析 43
4.1.2.2 觸媒酸活性種類分析 48
4.1.3穿透式電子顯微鏡 51
4.1.5觸媒分析論述 56
4.2 醯化反應檢測 58
4.2.1 茴香醚之醯化反應 60
4.2.2 藜蘆醚之醯化反應 68
第五章 結論 73
參考文獻 75
附錄 78

B1.陳郁文，劉瑞祺合譯，“化學反應工程原理”3rd，台北：東華書局，(2000)， pp. 628
B2.Jens Hagen, “Industrial Catalysis :(A Practical Approach)”, WILEY-VCH, (2006), pp. 27-63
B3.Niek J. Ronde., “Catalysts for Continuous Homogeneous Catalysis”, Technische Universiteit Eindhoven, (2004), pp. 1-3.
B4.J.C. Bailar, “The Chemistry of the Coordination Compounds”, Reinhold Publishing Corporation, (1956), pp. 472-482
B5.G. C. Bond, “Heterogeneous Catalysis : Principles and Applications” (second edition), Oxford University Press, (1987), pp. 6-42.
B6.Charies N.Satterfield, “Heterogeneous catalysis in industrial practice” (second edition), McGraw-Hill, (1991), pp. 183-207
B7.Roger Arthur Sheldon, Hermann van Bekkum, “Fine chemicals through heterogenous catalysis”, WILEY-VCH, (2001), pp. 100-105
B8.Trimm, D.L., “Design of Industrial Catalysts”, Elsever, Amsterdam, (1980), pp. 7-63
1.李佳融，“以溶凝膠法製作 SiO2 奈米多孔質載體之加工特性的初步探討”，碩士論文，國立交通大學,新竹 (2001)
2.柯惠馨，“金屬氧化物及奈米級中孔洞矽鋁分子篩固體酸觸媒之製備修飾與鑑定”，碩士論文，中國文化大學, 台北(2005)
3.M. Misono, “Selective catalytic reactions and separations : Oiso, Japan, 1–5.February 1988”, Applied Catalysis, Volume 45, Issue 1, (1988), pp. 158
4.M. Misono, T. T. Okuhara, N. Mizuno, “Catalysis by Heteropoly Compounds”, Studies in Surface Science and Catalysis, Volume 44, (1989), P. 267-278
5.W. Xu, J. Dong, J. Li, J. Li and F. Wu, J., “A novel method for the preparation of zeolite ZSM-5”, Chem. Soc., Chem. Commun., (1990), pp. 755.
6.I.V. Kozhevnikov, K.I. Matveev, “Homogeneous catalysts based on heteropoly acids”, Applied Catalysis, Volume 5, Issue 2, (1983), pp. 135-150
7.J. Poz′niczek, A. Luban′ska, A. Micek-Ilnicka, D. Mucha, E. Lalik, A. Bielan′ski, “TiO2 and SiO2 supported Wells-Dawson heteropolyacid H6P2W18O62 as the catalyst for ETBE formation”, Applied Catalysis A: General, (2006), pp. 217–224
8.Bulcsu′ Ra′c, Gabriele Mulas, Aniko′ Csongra′di, Katalin Lo′ki, A′ rpa′d Molna′r, “SiO2-supported dodecatungstophosphoric acid and Nafion-H prepared by ball-milling for catalytic application”, Applied Catalysis A: General, (2005), pp. 255–265
9.D.H. Jung, S.Y. Cho, D.H. Peck, D.R. Shin, J.S. Kim, “Performance evaluation of a Nafion/silicon oxide hybrid membrane for direct methanol fuel cell”, Journal of Power Sources, (2002), pp. 173–177
10.Zhiqiang Sun, Jie Xu, Zhongtian Du, Wei Zhang, “Decomposition of cyclohexyl hydroperoxide over transition metal-free zeolite H-beta”, Applied Catalysis A: General, (2007), pp. 119–125
11.M.H. Kim., H.X. Li, M.E. Davis, “Synthesis of zeolites by water-organic vapor-phase transport”, Microporous Mater., (1993), pp. 191-200
12.M. Matsukata, N. Nishiyama and K. Ueyama, “Synthesis of zeolites under vapor atmosphere. Effect of synthetic conditions on zeolite structure”, Microporous Mater., (1993), pp. 219-222
13.Masahiko Matsukata, Norikazu Nishiyama, Korekazu Ueyama, “Crystallization of FER and MFI zeolites by a vapor-phase transport method”, Microporous Materials 7, (1996), pp. 109-117
14.P.R. Hari Prasad Raoa, K. Ueyamaa, M. Matsukatab, “Crystallization of high silica BEA by dry gel conversion”, Applied Catalysis A: General 166, (1998), pp. 97-103
15.I.V. Kozhevnikov, “Friedel–Crafts acylation and related reactions catalysed by heteropoly acids”, Applied Catalysis A: General, (2003), pp. 3–18
16.G. Bond, J.A. Gardner, R.W. McCabe, D.J. Shorrock, “Friedel-Crafts acylation reactions using heterogeneous catalysts stimulated by conventional and microwave heating”, Journal of Molecular Catalysis A: Chemical, (2007), pp. 1–5
17.J. Kaur, K. Griffin, B. Harrison, I. V. Kozhevnikov, “Friedel–Crafts Acylation Catalysed by Heteropoly Acids”, Journal of Catalysis, (2002), pp. 448–455
18.Luiz A.M. Cardoso, Walter Alves. Jr., Angélica R.E. Gonzaga, Leila M.G. Aguiar, Heloysa M.C. Andrade, “Friedel–Crafts acylation of anisole with acetic anhydride over silica-supported heteropoly phosphotungstic acid (HPW/SiO2)”, Journal of Molecular Catalysis A: Chemical, (2004), pp. 189–197
19.I.V. Kozhevnikov, “Heterogeneous acid catalysis by heteropoly acids: Approaches to catalyst deactivation”, Journal of Molecular Catalysis A: Chemical, (2009), pp. 104-111
20.C. Guignard, V. Pédron, F. Richard, R. Jacquot, M. Spagnol, J.M. Coustard, G. Pérot, “Acylation of veratrole by acetic anhydride over Hβand HY zeolites Possible role of di- and triketone by-products in the deactivation process”, Applied Catalysis A: General, (2002), pp. 79–90
21.A. Bred, M. Signoretto, E. Ghedini, F. Pinna, G. Cruciani, “Acylation of veratrole over promoted SZ/MCM-41 catalysts: Influence of metal promotion”, Applied Catalysis A: General, (2006), pp. 216–222
22.Ankur Bordoloi, Nevin T. Mathew, Biju M. Devassy, S.P. Mirajkar, S.B. Halligudi, “Liquid-phase veratrole acylation and toluene alkylation over WOx/ZrO2 solid acid catalysts”, Journal of Molecular Catalysis A: Chemical, (2006), pp. 58–64
23.Nilesh G. Waghmare, Palraj Kasinathan, Amol Amrute, Nishita Lucas, S.B. Halligudi, “Titania supported silicotungstic acid: An efficient solid acid catalyst for veratrole acylation”, Catalysis Communications, (2008), pp. 2026–2029
24.B. Bachiller-Baeza, J.A. Anderson, “FTIR and reaction studies of the acylation of anisole with acetic anhydride over supported HPA catalysts”, Journal of Catalysis, (2004), pp. 225–233
25.K.M. Parida, Sujata Mallick, G.C. Pradhan, “Acylation of anisole over 12-heteropolyacid of tungsten and molybdenum promoted zirconia”, Journal of Molecular Catalysis A: Chemical 297, (2009), pp.93–100