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研究生： 林秋杏
Chiu-Hsing Lin
論文名稱： 金催化劑進行甲醇重組反應來製造氫氣
Hydrogen Production by Reforming of Methanol over Au Catalysts
指導教授： 葉君棣
Chuin-Tih Yeh
口試委員:
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2006
畢業學年度： 94
語文別： 中文
論文頁數： 78
中文關鍵詞： 沉積沉澱法 、金催化劑 、甲醇部分氧化反應 、甲醇蒸氣重組反應
外文關鍵詞： deposition precipitateon method, Au catalyst, partial oxidation of methanol POM, steam reforming of methanol，SRM
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    • 本研究以沉積沉澱法 (deposition precipitateon method) 製備以氧化鋅為支撐物的金催化劑。並利用XRD、TEM、ICP、TPR等方法來鑑定催化劑的物理與化學特性。並將製備好的催化劑用於催化甲醇重組反應: 反應包括部分氧化反應 (partial oxidation of methanol POM)、蒸氣重組反應 (steam reforming of methanol，SRM)、氧化性蒸氣重組反應 (oxidative steam reforming of methanol，OSRM)。
    金催化劑用於催化SRM與OSRM的效果不佳，但在催化POM上則有良好的活性。以表面積為43 m2/g的氧化鋅為支撐物並添加1%鈰的金催化劑，於POM反應中擁有最佳的活性表現，在反應溫度(reaction temperature，TR )為150℃時，CMeOH = 86％，SH2 = 88％，SCO2 = 98％。
    為了使POM反應可在不需要額外加熱時，就有良好的活性表現，我們將通過金催化劑的甲醇量提高為原來的1.5倍來進行反應。結果證實此方式可將反應溫度維持於120℃，並且擁有良好的活性，CMeOH = 90％，SH2 = 91％，SCO2 = 98％。

    In this study, supported of Au2/Zn or Au2Cex/Zn samples were prepared by deposition precipitation method. All samples were characterized by XRD, TEM, ICP and TPR measurements. These catalysts were applied for reforming of methanol reactions, including partial oxidation of methanol (POM), steam reforming of methanol (SRM) and oxidative steam reforming of methanol (OSRM).
    Au/Zn catalysts were not active for SRM and OSRM reactions, but active for POM reaction. Au2Ce1/Zn supported on ZnO with surface area of 43 m2/g shows the best performance (CMeOH = 86％, SH2 = 88％, SCO2 = 98％) of POM at TR = 150℃.
    When the amount of methanol is increased by 1.5 times in POM reaction for Au2Ce1/Zn catalyst, the reaction temperature could maintain at 120℃ without an additional heater. Moreover, there is a excellent performance (CMeOH = 90％, SH2 = 91％, SCO2 = 97.3％) of POM reaction at 120℃.

    第一章 緒論 1 1-1 前言 1 1-2 燃料電池 1 1-3 氫氣的供應、儲存與運輸 3 1-4 甲醇重組來製造氫氣 6 1-5 文獻回顧 11 1-5.1 金催化劑 11 1-5.2 甲醇重組反應製氫 12 1-5.3 氧化鈰促進劑 16 1-5.4 氧化鋅 19 1-6 研究目的及方向 20 第二章 實驗 21 2-1 藥品 21 2-2 金催化劑的製備 22 2-2.1製備支撐物氧化鋅 22 2-2.2 以沈積沈澱法（DP）製備金催化劑 22 2-2.3 催化劑的還原前處理 22 2-3 催化劑的特性鑑定 23 2-3.1 X光粉末繞射儀 (XRD) 23 2-3.2 穿透式電子顯微鏡 (TEM) 23 2-3.3 程溫還原反應 (TPR) 23 2-3.4 表面積測量 (BET) 24 2-3.5 元素分析 (ICP-AES) 25 2-4 催化劑的甲醇重組反應活性測試 25 第三章 結果與討論 33 3-1氧化鋅支撐物的特性分析 33 3-1-1表面積的量測（BET） 33 3-1-2 X光粉末繞射（XRD） 33 3-2金催化劑的特性分析 36 3-2.1樣品的簡稱 36 3-2.2金屬的負載量 36 3-2.3 X光粉末繞射 (XRD) 38 3-2.4 TEM的物性鑑定 41 3-2.5程溫還原分析 (TPR) 46 3-3金催化劑的催化活性 49 3-3.1反應溫度對POM反應活性的影響 49 3-3.2氧化鋅表面積對POM反應活性的影響 51 3-3.3鈰添加量對POM反應活性的影響 51 3-3.4氧醇比 (x = nO2/nMeOH) 對POM反應活性的影響 53 3-3.5金催化劑對POM 反應活性衰退測試 57 3-3.6改變甲醇流速對POM 反應活性的影響 57 3-4金催化劑進行POM反應的反應機制 60 3-5金催化劑進行SRM及OSRM反應之活性 63 3-6 未來研究方向 69 第四章 結論 70 第五章 參考文獻 71

    [1] S. Velu, K. Suzuki, M. Okazaki, M. P. Kapoor, T. Osaki, F. Ohashi, J. Catal., 194 (2000) 373.
    [2] T. Klaiber, J. Power Sources, 61 (1996) 61.
    [3] P. Ekdunge, M. Råberg, Int. J. Hydrogen Energy, 23 (1998) 381.
    [4] W. J. Piel, Fuel Processing Technology, 71 (2001) 167.
    [5] M. Specht, F. Staiss, A. Bandi, T. Weimer, Int. J. Hydrogen Energy, 23 (1998) 387.
    [6] B. Höhlein, J. Bøgild-Hansen, P. Bröckerhoff, G. Colsman, B. Emonts, R. Menzer, E. Riedel, J. Power Sources, 61 (1996) 143.
    [7] A. Docter, A. Lamm, J. Power Sources, 84 (1999) 194.
    [8] 葉君棣, 科學人, 12 (2002) 52.
    [9] A. K. Shukla, P. A. Christensen, A. Hamnett, M. P. Hogarth, J. Power Sources, 55 (1995) 87.
    [10] G. G. Scherer, Solid State Ionics, 94 (1997) 249.
    [11] B. Linström, L. J. Pettersson, Catal. Lett., 74 (2001) 27.
    [12] P. X. Hou, Q. H. Tang, S. Bai, S. T. Xu, M. Liu, H. M. Cheng, J. Phys. Chem. B, 106 (2002) 963.
    [13] A. Chamber, C. Park, R. T. Baker, N. M. Rodriguez, J. Phys. Chem. B, 102 (1998) 4253.
    [14] F. Joensen, J. R. Rostrup-Nielsen, J. Power Sources, 105 (2002) 195.
    [15] C. R. Manns, C. E. Taylor, Furl Chemistry Division Perprints, 46 (2001) 6.
    [16] D. J. Moon, K. Sreekumar, S. D. Lee, B. G. Lee, H. S. Kim, Appl. Catal. A: General, 215 (2001) 1.
    [17] A. S. Arico, P. Creti, P. L. Antonucci, V. Antonucci, Electrochemical and Soild-State Letters, 1 (1998) 66.
    [18] Bård Lindström, Lars J. Pettersson, Int. J. Hydrogen Energy, 26 (2001) 923.
    [19] J. R. Rostrup-Nielsen, T. S. Christensen, I. Dybkjaer, Recent Advances in Basic and Applied Aspects of Industrial Catalysis, 113 (1998) 81.
    [20] T. Takahashi, M. Inoue, T. Kai, Appl. Catal. A: General, 218 (2001) 189.
    [21] Y. M. Lin, M. H. Rei, Int. J. Hydrogen Energy, 25 (2000) 211.
    [22] W. Wiese, B. Enonts, R. Peters, J. Power Source, 84 (1999) 187.
    [23] N. Takezawa, N. Iwasa, Catal. Today, 36 (1997) 45.
    [24] C. J. Jiang, D. L. Trimm, M. S. Wainwright, Appl. Catal. A: General, 97 (1993) 145.
    [25] T. L. Reitz, S. Ahmed, M. Krumpelt, R. Kumar, H. H. Kung, J. Mole. Catal. A Chemical, 162 (2000) 275.
    [26] S. Velu, K. Suzuki, M. P. Kapoor, F. Ohashi, T. Osaki, Appl. Catal. A: General, 213 (2001) 47.
    [27] S. Murcia-Mascaròs, R. M. Navarro, L. Gòmez-Sainero, U. Costantino, M. Nocchetti, J. L.G. Fierro, J. Catal., 198 (2001).
    [28] Gregor Hoogers, Fuel Cell technology handbook.
    [29] K. Selizawa, S. I. Yano, K. Eguchi, H. Arai, Appl. Catal. A: General, 169 (1998) 291.
    [30] B. Emonts, J. B. Hansen, S. L. Jørgensen, B. Höhlein, R. Peters, J. Power Sources, 71 (1998) 288.
    [31] F. Boccuzzi, A. Chiorino, M. Manzoli, D. Andreeva, T. Tabakova, L. Ilieva, V. Iadakiev, Catal. Today, 75 (2002) 169.
    [32] G. Avgouropoulos, T. Ioannides, Ch. Papadopoulou, J. Batista, S. Hocevar, H. K. Matralis, Catal. Today, 75 (2002) 157.
    [33] J. Schwank, Gold Bull., 16 (1983) 103.
    [34] I. E. Wachs, Gold Bull, 16 (1983) 98.
    [35] M. Haruta, N. Yamada, T. Kobayahsi, S. Iijima, J. Catal., 115 (1989) 301.
    [36] M. Haruta, in:R. K. Grasselli et al., Eds., 3rd World Congress on Oxidation Cataysis, Elsevier Science B. V., (1997) 123.
    [37] S. Tsubato, M. Haruta, A. Uea and Y. Nakahara, in:G. Poncelet et al.,
    Eds., Preparation of Catalysts V, Elsevier Science B. V., (1991) 695.
    [38] T. Kobayashi, M. Haruta, S. Tsubato and H. Sano, Sensors and Actuators, B1 (1990) 222.
    [39] M. Okumura, K. Tanaka, A. Ueda and M. Haruta, Solid State Ionics, 95 (1997) 143.
    [40] Q. Jiang, S. Zhang, M. Zhao, Materials Chemistry and Physics 82 (2003) 225–227.
    [41] F. W. Chang, T. C. Ou, Applied Catalysis A: General 302 (2006)
    157.
    [42] M. Haruta, S. Tsubato, T. Kobayashi, H. Kageyama, M. J. Genet, B. Delmon, J. Catal., 144 (1993) 175.
    [43] M. Haruta, T. Kobayashi, S. Tsubato, Y. Nakahara, Chem. Express, 5 (1988) 159.
    [44] S. Tsubato, N. Tamada, M. Haruta, T. Kobayashi, Y. Nakahara, Chem. Express, 5 (1991) 349.
    [45] D. Andreeva, I. Ivanov , L. Ilieva , M.V. Abrashev, Applied Catalysis A: General, 302 (2006) 127.
    [46] R. D. Waters, J. J. Weimer, J. E. Smith, Catal. Lett., 30 (1995) 181.
    [47] A. Ueda, M. Haruta, Shigen Kankyo Taisaku, Resources and Environment, 28 (1992) 1035.
    [48] R. Nakamura, S. Suzuki, R. Aida, H. Niiyama, Proc. 24th Meet, Chem. Engng. Soc. Jap., 1 (1991) 166.
    [49] T. Hayashi, M. Haruta, Shokubai, Catalysts and Catalysis, 37 (1995) 72.
    [50] H. Sakurai, S. Tsubota, M. Haruta, Appl. Catal. A: General, 102 (1993) 125.
    [51] J. C. Frost, Nature, 334 (1988) 577.
    [52] D. A. Buchanan, G. Webb, J. Chem. Soc. Faraday I, 70 (1978) 134.
    [53] M. Shibata, N. Kawata, T. Masumoto, H. Kimura, Japan-France Seminar on Catalysis with Metal Compounds, Tokyo, pp. 98-100 (1987).
    [54] A. Ueda, M. Haruta, Appl. Catal. B: Environment, 69 (1997) 258.
    [55] T. Aida, R. Higuchi, H. Niiyama, Chem. Lett., (1990) 2247.
    [56] B. Chen, C. Bai, R. Cook, J. Wright, 14th North American Meeting of the Catalysis Society, Snowbird, Utah, June, T7-8 (1995).
    [57] Y. Takita, T. Imamura, Y. Mizuhara, Y. Abe, T. Ishihara, Appl. Catal.
    B: Environmental, 1 (1992) 79.
    [58] J. Agrell, K. Hasselbo, K. Jansson, S. G. Jaras, M. Boutonnet, Appl. Catal. A: General, 211 (2001) 239.
    [59] S. Velu, K. Suzuki, T. Osaki, Catal. Lett., 62 (1999) 159.
    [60] 洪華聖，清華大學碩士論文 (2002).
    [61] 趙科量，清華大學碩士論文 (2005).
    [62] 陳永杰，清華大學博士論文 (2006).
    [63] L. Mo, X. Zheng, C. T. Yeh, Chem. Comm., (2004) 1426.
    [64] 萬厚德，清華大學碩士論文(2003).
    [65] Cubeiro, J. L. G. Fierro, Appl. Catal. A: General, 168 (1998) 307.
    [66] S. Velu, K. Suzuki, M. Okazaki, M. P. Kapoor, T. Osaki, F. Ohashi, J. Catal., 194 (2000) 373.
    [67] S. Velu, K. Suzuki, Top. Catal., 22 (2003) 235.
    [68] I. S. Metcalfe and S. Sundaresan, AIChE J., 34 (198) 195.
    [69] R. G. Silver, C. J. Hou and J. G. Ekerdt, J. Catal., 118 (1989) 400.
    [70] N. B. Jackson and J. G. Ekerdt, J. Catal., 126 (1990) 31.
    [71] B. K. Cho, J. Catal., 131 (1991) 74.
    [72] W.-P. Dow and T.-J. Huang, J. Catal., 147 (1994) 322.
    [73] W.-P. Dow, Y.-P. Wang and T.-J. Huang, J. Catal., 160 (1996) 155.
    [74] W.-P. Dow and T.-J. Huang, J. Catal., 160 (1996)171.
    [75] P. A. Dilara and J.M. Vohs, J. Phys. Chem., 97 (1993) 12919.
    [76] G. Avgouropoulos, T. Ioannides, Appl. Catal. A: General, 244 (2003) 155.
    [77] J. B. Wang, S. C. Lin, T. J. Huang, Appl. Catal. A: General, 232 (2002) 107.
    [78] B. G. Mishra, G. R. Rao, Bull. Mater. Sci., 25 (2002) 155.
    [79] R. M. Ferrizz, G. S. Wong, T. Egami, J. M. Vohs, Langmuir, 17 (2001) 2464.
    [80] Lijun Wu, H. J. Wiesmann, A. R. Moodenbaugh, R. F. Klie, Yimei Zhu, D. O. Welch, M. Suenaga, Phys. Rev. B, 69 (2004) 125415.
    [81] B. Na, A. Walters, M. Vannice, J. Catal., 140 (1993) 585.
    [82] E. A. Meulenkamp, J. Phys. Chem. B, 102 (1998) 5566.
    [83] C. L. Carnes, K. J. Klabunde, Langmuir, 16 (2000) 3767.
    [84] D. Mondelaers, G. Vanhoyland, H. Van den Rul, J. D’Haen, M.K. Ban Bael, J. Mullens, L. C. Van Poucke, Mater. Res. Bull., 37 (2002) 901.
    [85] T. Fujitani, J. Nakamura, Catal. Lett., 56 (1998) 119.
    [86] N. Iwasa, T. Mayanagi, W. Nomura, M. Arai, N. Takezawa, Appl. Catal. A: General, 248 (2003) 153.
    [87] The Merck Index, Merck & Co., (1996).
    [88] 何永盛，清華大學博士論文(1980).
    [89] W. K. Chen, S. H. Liu, M. J. Cao, Q. G. Yan, C. H. Lu, Journal of Molecular Structure: THEOCHEM, (2006) 1.

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