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研究生: 曹恩榮
En-Rong Cao
論文名稱: 利用油胺製備鑭鈰鋯氧化物擔載鎳觸媒 應用於蒸氣重組製氫反應
Surfactant Assisted Nickel Catalysts for Hydrogen production by steam reforming
指導教授: 林昇佃
Shawn D. Lin
口試委員: 胡哲嘉
Che-Chia Hu
游文岳
Wen-Yueh Yu
鍾博文
Po-Wen Chung
學位類別: 碩士
Master
系所名稱: 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年: 2023
畢業學年度: 111
語文別: 中文
論文頁數: 109
中文關鍵詞: 鎳觸媒蒸氣重組微胞
外文關鍵詞: Nickel catalyst, steam reforming, hydrogen production, micelles
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  • 氫能源在未來被視為一種相當具有潛力的能源,因為它的能量密度高,且使用過程不會造成污染,而甲烷蒸氣重組仍然是工業上用來製造氫氣的方法,鎳觸媒應用在此反應時,雖然有價格低以及活性高的優勢,但是在高溫時會受到積碳以及燒結問題影響。本實驗室先前研究將鎳擔載於LaZrCeOX(LZC)螢石結構的金屬氧化物載體上,發現Ni/LZC觸媒可減少積碳、燒結現象,且具有良好活性,但結果顯示當鎳含量小於10 wt%時,Ni/LZC會因比表面積過低而失去活性。本研究在共沉澱法製備觸媒時加入油胺(oleylamine),期望觸媒能與油胺形成的微胞一起沉澱,再藉由鍛燒程序將微胞移除,實驗結果顯示添加油胺後,觸媒的晶體結構並無顯著影響,載體與鎳的結晶大小皆為4-5 nm,但BET結果顯示觸媒的比表面積隨著油胺添加量增加而上升,添加0.1 M油胺的觸媒比表面積上升至99.9 m2/g,同時也觀察到有約10 nm的孔洞生成,TPD、TEM結果發現觸媒的顆粒堆疊現象減少、活性金屬的分散度也有增加,比較油胺添加對Ni/LaZrCeOx觸媒在甲烷蒸氣重組的測試中,結果顯示油胺並不會導致觸媒反應性的改變,並研究將5% Ni/LZC_OAm0.1應用於丙烷及甘油蒸氣重組也呈現出良好的斷C-C鍵能力在600°C時兩反應皆可達到完全轉化,於丙烷蒸氣重組時與27.9% Ni/LZC有相同的活化能與TOF,且與文獻相比時發現Ni/LZC有較低的活化能≈ 62 kJ/mol,但是仍有明顯積碳現象的發生,而Ni/LZC在甘油蒸氣重組時相對於文獻也有高CO2選擇率以及H2產率,對於將甘油轉化為氣相產物能力優異,且由於反應機制的差異造成以甘油做為蒸氣重組的反應物時相對丙烷,減少了產物中CH4的占比以及積碳的現象。


    Hydrogen energy serves as potential energy in our future. The methane steam reforming reaction is still the industry's most used method for hydrogen production. The use of nickel catalysts is significant in this reaction due to their affordable cost and high reactivity. However, they tend to face a severe coking issue at high temperatures. In our research using Nickel loading on LaZrCeOX(LZC), LaZrCeOX is a mixed metal oxide support with a fluorite structure, we found that Ni/LZC has high thermal stability and coking resistance ability, Our laboratory has found that a Nickel loading of less than 10 wt% in the catalyst results in a decrease in activity due to a low specific surface area (<1 m2/g). This study aims to improve the 5% Ni/LZC reactivity on methane steam reforming by increasing the specific area. Using Co-Precipitation to prepare the catalyst, adding oleylamine during preparation. It is expected that the micelles formed by oleylamine can occupy space on the catalyst during precipitation and be removed by calcination. Using different concentrations of oleylamine to make the comparison. The BET result shows that the surface area of the catalyst increases with the additional amount of oleylamine. Also, in the BJH results 10 nm pores were formed. The TEM、H2-TPD and EXAFS results show that the catalyst with oleylamine addition reduced the stacking of catalyst particles and increase the dispersion of active metal. Activity tests show that 5% Ni/LZC_OAm0.1 has better reactivity and no serious coking tendency during methane steam reforming.
    Apply 5% Ni/LZC_OAm0.1 to propane and glycerol steam reforming. We found that it shows a good ability to break carbon bonds in the structure of propane and glycerol both achieving 100% conversion at 600°C. In propane steam reforming, 5% Ni/LZC_OAm0.1 has the same activation energy and TOF as 27.9% Ni/LZC, also found that Ni/LZC has a lower activation energy than the literature reported. But it still has coking formation at 600°C. In glycerol steam reforming Ni/LZC also performs a good activity it has 100% glycerol conversion and a high H2 Yield at 600°C.

    摘要 I Abstract III 誌謝 V 目錄 VI 圖目錄 IX 表目錄 XII 第1章 緒論 1 1.1 前言 1 1.2 文獻回顧 4 1.2.1 合成觸媒添加界面活性劑的影響 4 1.2.2 烷類蒸氣重組反應 5 1.2.3 甘油蒸氣重組 7 1.3 研究目的 9 第2章 研究架構與方法 10 2.1 研究架構 10 2.2 藥品與儀器設備 11 2.2.1 藥品 11 2.2.2 氣體 12 2.2.3 使用儀器 13 2.3 觸媒製備 14 2.3.1 共沉澱法製備Ni/LZC觸媒 14 2.3.2 共沉澱法製備Ni/LZC_OAmx 15 2.4 觸媒特性分析 16 2.4.1 X光粉末繞射儀 16 2.4.2 程溫還原反應 16 2.4.3 比表面積與孔隙測定儀 17 2.4.4 熱重分析儀 18 2.4.5 掃描式電子顯微鏡 18 2.4.6 穿透式電子顯微鏡 18 2.4.7 氫氣程溫脫附(H2-TPD) 19 2.4.8 烷類蒸氣重組反應 20 2.4.9 甘油蒸氣重組反應 21 第3章 添加油胺對共沉澱法合成Ni/LZC特性的影響 23 3.1 5% Ni/LZC_OAmx觸媒特性分析 23 3.1.1 觸媒姓質鑑定 24 3.1.2 油胺添加量於觸媒對甲烷蒸氣重組反應之影響 39 3.1.3 5% Ni/LZC_OAmx反應後觸媒鑑定 43 3.2 X% Ni/LZC_OAm0.05觸媒特性分析(X = 5, 10, 16.2) 47 3.2.1 觸媒性質鑑定 47 3.2.2 X% Ni/LZC_OAmx觸媒甲烷蒸氣重組反應 55 3.2.3 反應後觸媒鑑定 59 3.3 小結 62 第4章 Ni/LZC應用於丙烷以及甘油蒸氣重組 63 4.1 丙烷蒸氣重組 64 4.2 甘油蒸氣重組 74 4.3 甘油蒸氣重組反應與丙烷蒸氣重組反應之比較 79 4.4 小結 85 第5章 結論 86 參考文獻 87 第六章 附錄 94

    [1] E. Dahdah, J. Estephane, C. Gennequin, A. Aboukaïs, S. Aouad, and E. Abi-Aad, "Effect of La promotion on Ni/Mg-Al hydrotalcite derived catalysts for glycerol steam reforming," Journal of Environmental Chemical Engineering, vol. 8, no. 5, p. 104228, 2020.
    [2] X. Zhang et al., "Platinum–copper single atom alloy catalysts with high performance towards glycerol hydrogenolysis," Nature communications, vol. 10, no. 1, p. 5812, 2019.
    [3] A. Abdullah et al., "A review on recent developments and progress in sustainable acrolein production through catalytic dehydration of bio-renewable glycerol," Journal of Cleaner Production, vol. 341, p. 130876, 2022.
    [4] G. Wu, S. Li, C. Zhang, T. Wang, and J. Gong, "Glycerol steam reforming over perovskite-derived nickel-based catalysts," Applied Catalysis B: Environmental, vol. 144, pp. 277-285, 2014.
    [5] E. Dahdah, J. Estephane, C. Gennequin, A. Aboukais, E. Abi-Aad, and S. Aouad, "Zirconia supported nickel catalysts for glycerol steam reforming: Effect of zirconia structure on the catalytic performance," International Journal of Hydrogen Energy, vol. 45, no. 7, pp. 4457-4467, 2020.
    [6] Y.-C. Lin, "Catalytic valorization of glycerol to hydrogen and syngas," international journal of hydrogen energy, vol. 38, no. 6, pp. 2678-2700, 2013.
    [7] D. Myers, Surfactant science and technology. John Wiley & Sons, 2020.
    [8] H. Wennerström and B. Lindman, "Micelles. Physical chemistry of surfactant association," Physics Reports, vol. 52, no. 1, pp. 1-86, 1979.
    [9] D. Terribile, A. Trovarelli, J. Llorca, C. de Leitenburg, and G. Dolcetti, "The preparation of high surface area CeO2–ZrO2 mixed oxides by a surfactant-assisted approach," Catalysis Today, vol. 43, no. 1-2, pp. 79-88, 1998.
    [10] 廖全奎, "添加界面活性劑對共沉澱法製備 Ni/LZC 觸媒結構的影響," 國立臺灣科技大學, 台北市, 2021.
    [11] H. Zhang, Z. Sun, and Y. H. Hu, "Steam reforming of methane: Current states of catalyst design and process upgrading," Renewable and Sustainable Energy Reviews, vol. 149, p. 111330, 2021.
    [12] H. Wu, V. La Parola, G. Pantaleo, F. Puleo, A. M. Venezia, and L. F. Liotta, "Ni-based catalysts for low temperature methane steam reforming: recent results on Ni-Au and comparison with other bi-metallic systems," Catalysts, vol. 3, no. 2, pp. 563-583, 2013.
    [13] S. D. Angeli, L. Turchetti, G. Monteleone, and A. A. Lemonidou, "Catalyst development for steam reforming of methane and model biogas at low temperature," Applied Catalysis B: Environmental, vol. 181, pp. 34-46, 2016.
    [14] E. T. Kho, J. Scott, and R. Amal, "Ni/TiO2 for low temperature steam reforming of methane," Chemical Engineering Science, vol. 140, pp. 161-170, 2016.
    [15] Y. Matsumura and T. Nakamori, "Steam reforming of methane over nickel catalysts at low reaction temperature," Applied Catalysis A: General, vol. 258, no. 1, pp. 107-114, 2004.
    [16] 林力雋, "混合氧化物擔載鎳觸媒應用於中溫甲烷蒸汽重組反應," 碩士, 化學工程系, 國立臺灣科技大學, 台北市, 2016.
    [17] J. N. Heo, N. Son, J. Shin, J. Y. Do, and M. Kang, "Efficient hydrogen production by low-temperature steam reforming of propane using catalysts with very small amounts of Pt loaded on NiMn2O4 particles," International Journal of Hydrogen Energy, vol. 45, no. 41, pp. 20904-20921, 2020.
    [18] A. Kokka, A. Katsoni, I. V. Yentekakis, and P. Panagiotopoulou, "Hydrogen production via steam reforming of propane over supported metal catalysts," International Journal of Hydrogen Energy, vol. 45, no. 29, pp. 14849-14866, 2020.
    [19] T. Ramantani, V. Evangeliou, G. Kormentzas, and D. I. Kondarides, "Hydrogen production by steam reforming of propane and LPG over supported metal catalysts," Applied Catalysis B: Environmental, vol. 306, p. 121129, 2022.
    [20] R. Arvaneh, A. A. Fard, A. Bazyari, S. M. Alavi, and F. J. Abnavi, "Effects of Ce, La, Cu, and Fe promoters on Ni/MgAl 2 O 4 catalysts in steam reforming of propane," Korean Journal of Chemical Engineering, vol. 36, pp. 1033-1041, 2019.
    [21] C. A. Schwengber et al., "Overview of glycerol reforming for hydrogen production," Renewable and Sustainable Energy Reviews, vol. 58, pp. 259-266, 2016.
    [22] A. Iriondo et al., "Glycerol steam reforming over Ni catalysts supported on ceria and ceria-promoted alumina," international journal of hydrogen energy, vol. 35, no. 20, pp. 11622-11633, 2010.
    [23] K. N. Papageridis et al., "Comparative study of Ni, Co, Cu supported on γ-alumina catalysts for hydrogen production via the glycerol steam reforming reaction," Fuel Processing Technology, vol. 152, pp. 156-175, 2016.
    [24] P. D. Vaidya and A. E. Rodrigues, "Glycerol reforming for hydrogen production: a review," Chemical Engineering & Technology: Industrial Chemistry‐Plant Equipment‐Process Engineering‐Biotechnology, vol. 32, no. 10, pp. 1463-1469, 2009.
    [25] G. Wu et al., "Hydrogen production via glycerol steam reforming over Ni/Al2O3: influence of nickel precursors," ACS Sustainable Chemistry & Engineering, vol. 1, no. 8, pp. 1052-1062, 2013.
    [26] S. Shao, A.-W. Shi, C.-L. Liu, R.-Z. Yang, and W.-S. Dong, "Hydrogen production from steam reforming of glycerol over Ni/CeZrO catalysts," Fuel Processing Technology, vol. 125, pp. 1-7, 2014.
    [27] 余登立, "鑭鋯鈰缺陷螢石結構載體擔載鎳鈷觸媒 應用於中溫甲烷重組反應," 碩士, 化學工程系, 國立臺灣科技大學, 台北市, 2019.
    [28] X. Gao, H. Liu, K. Hidajat, and S. Kawi, "Anti‐coking Ni/SiO2 catalyst for dry reforming of methane: Role of oleylamine/oleic acid organic pair," ChemCatChem, vol. 7, no. 24, pp. 4188-4196, 2015.
    [29] L. Li, D. Mao, J. Yu, and X. Guo, "Highly selective hydrogenation of CO2 to methanol over CuO–ZnO–ZrO2 catalysts prepared by a surfactant-assisted co-precipitation method," Journal of Power Sources, vol. 279, pp. 394-404, 2015.
    [30] K. Tripathi, R. Singh, and K. K. Pant, "Tailoring the physicochemical properties of Mg promoted catalysts via one pot non-ionic surfactant assisted co-precipitation route for CO2 Co-feeding syngas to methanol," Topics in Catalysis, vol. 64, no. 5, pp. 395-413, 2021.
    [31] M. Koopaie, "Nanoparticulate systems for dental drug delivery," in Nanoengineered Biomaterials for Advanced Drug Delivery: Elsevier, 2020, pp. 525-559.
    [32] X. Fang et al., "Highly active and stable Ni/Y2Zr2O7 catalysts for methane steam reforming: On the nature and effective preparation method of the pyrochlore support," international journal of hydrogen energy, vol. 41, no. 26, pp. 11141-11153, 2016.
    [33] D. S. M. S. Hosseini, H. Hashemipour, and A. Talebizadeh, "Oleylamine-modified impregnation method for the preparation of a highly efficient Ni/SiO2 nanocatalyst active in the partial oxidation of methane to synthesis gas," Chemical Industry and Chemical Engineering Quarterly, vol. 23, no. 2, pp. 259-267, 2017.
    [34] S.-J. Li, H.-L. Wang, J.-M. Yan, and Q. Jiang, "Oleylamine-stabilized Cu0. 9Ni0. 1 nanoparticles as efficient catalyst for ammonia borane dehydrogenation," International Journal of Hydrogen Energy, vol. 42, no. 40, pp. 25251-25257, 2017.
    [35] Y. Liu et al., "Catalytic methanation of syngas over Ni-based catalysts with different supports," Chinese journal of chemical engineering, vol. 25, no. 5, pp. 602-608, 2017.
    [36] W. C. Conner Jr and J. L. Falconer, "Spillover in heterogeneous catalysis," Chemical reviews, vol. 95, no. 3, pp. 759-788, 1995.
    [37] V. M. Gonzalez-Delacruz, R. Pereniguez, F. Ternero, J. P. Holgado, and A. Caballero, "Modifying the size of nickel metallic particles by H2/CO treatment in Ni/ZrO2 methane dry reforming catalysts," Acs Catalysis, vol. 1, no. 2, pp. 82-88, 2011.
    [38] A. Jentys, "Estimation of mean size and shape of small metal particles by EXAFS," Physical Chemistry Chemical Physics, vol. 1, no. 17, pp. 4059-4063, 1999.
    [39] W.-S. Dong, H.-S. Roh, K.-W. Jun, S.-E. Park, and Y.-S. Oh, "Methane reforming over Ni/Ce-ZrO2 catalysts: effect of nickel content," Applied Catalysis A: General, vol. 226, no. 1-2, pp. 63-72, 2002.
    [40] 洪晟耀, "應用於烷類重組製氫的低積碳潛勢鎳觸媒研究," 碩士, 化學工程系, 國立臺灣科技大學, 台北市, 2021.
    [41] M. L. Dieuzeide, M. Laborde, N. Amadeo, C. Cannilla, G. Bonura, and F. Frusteri, "Hydrogen production by glycerol steam reforming: How Mg doping affects the catalytic behaviour of Ni/Al2O3 catalysts," International Journal of Hydrogen Energy, vol. 41, no. 1, pp. 157-166, 2016.
    [42] A. Kokka, A. Petala, and P. Panagiotopoulou, "Support Effects on the Activity of Ni Catalysts for the Propane Steam Reforming Reaction," Nanomaterials, vol. 11, no. 8, p. 1948, 2021.
    [43] A. A. Fard, R. Arvaneh, S. M. Alavi, A. Bazyari, and A. Valaei, "Propane steam reforming over promoted Ni–Ce/MgAl2O4 catalysts: Effects of Ce promoter on the catalyst performance using developed CCD model," International Journal of Hydrogen Energy, vol. 44, no. 39, pp. 21607-21622, 2019.
    [44] A. Kokka, T. Ramantani, I. Yentekakis, and P. Panagiotopoulou, "Catalytic performance and in situ DRIFTS studies of propane and simulated LPG steam reforming reactions on Rh nanoparticles dispersed on composite MxOy-Al2O3 (M: Ti, Y, Zr, La, Ce, Nd, Gd) supports," Applied Catalysis B: Environmental, vol. 316, p. 121668, 2022.
    [45] Y. Im, J. H. Lee, B. S. Kwak, J. Y. Do, and M. Kang, "Effective hydrogen production from propane steam reforming using M/NiO/YSZ catalysts (M= Ru, Rh, Pd, and Ag)," Catalysis Today, vol. 303, pp. 168-176, 2018.
    [46] K. S. Park et al., "Adjusted interactions of nickel nanoparticles with cobalt-modified MgAl2O4-SiC for an enhanced catalytic stability during steam reforming of propane," Applied Catalysis A: General, vol. 549, pp. 117-133, 2018.
    [47] Y. Li, X. Wang, and C. Song, "Spectroscopic characterization and catalytic activity of Rh supported on CeO2-modified Al2O3 for low-temperature steam reforming of propane," Catalysis Today, vol. 263, pp. 22-34, 2016.
    [48] C. Resini, M. C. H. Delgado, L. Arrighi, L. J. Alemany, R. Marazza, and G. Busca, "Propene versus propane steam reforming for hydrogen production over Pd-based and Ni-based catalysts," Catalysis Communications, vol. 6, no. 7, pp. 441-445, 2005.
    [49] K. M. Kim, B. S. Kwak, N.-K. Park, T. J. Lee, S. T. Lee, and M. Kang, "Effective hydrogen production from propane steam reforming over bimetallic co-doped NiFe/Al2O3 catalyst," Journal of Industrial and Engineering Chemistry, vol. 46, pp. 324-336, 2017.
    [50] K. Kousi, D. Kondarides, X. Verykios, and C. Papadopoulou, "Glycerol steam reforming over modified Ru/Al2O3 catalysts," Applied Catalysis A: General, vol. 542, pp. 201-211, 2017.
    [51] M. Goula, N. Charisiou, K. Papageridis, and G. Siakavelas, "Influence of the synthesis method parameters used to prepare nickel-based catalysts on the catalytic performance for the glycerol steam reforming reaction," Chinese Journal of Catalysis, vol. 37, no. 11, pp. 1949-1965, 2016.
    [52] T. Hirai, N.-o. Ikenaga, T. Miyake, and T. Suzuki, "Production of hydrogen by steam reforming of glycerin on ruthenium catalyst," Energy & Fuels, vol. 19, no. 4, pp. 1761-1762, 2005.
    [53] B. Dou, C. Wang, Y. Song, H. Chen, and Y. Xu, "Activity of Ni–Cu–Al based catalyst for renewable hydrogen production from steam reforming of glycerol," Energy conversion and management, vol. 78, pp. 253-259, 2014.
    [54] O. Parlar Karakoc, M. Kibar, A. Akin, and M. Yildiz, "Nickel-based catalysts for hydrogen production by steam reforming of glycerol," International Journal of Environmental Science and Technology, vol. 16, pp. 5117-5124, 2019.
    [55] D. F. Suffredini et al., "Renewable hydrogen from glycerol reforming over nickel aluminate-based catalysts," Catalysis Today, vol. 289, pp. 96-104, 2017.
    [56] S. M. de Rezende, C. A. Franchini, M. L. Dieuzeide, A. M. D. de Farias, N. Amadeo, and M. A. Fraga, "Glycerol steam reforming over layered double hydroxide-supported Pt catalysts," Chemical Engineering Journal, vol. 272, pp. 108-118, 2015.
    [57] S. Adhikari, S. D. Fernando, S. F. To, R. M. Bricka, P. H. Steele, and A. Haryanto, "Conversion of glycerol to hydrogen via a steam reforming process over nickel catalysts," Energy & Fuels, vol. 22, no. 2, pp. 1220-1226, 2008.
    [58] I. N. Buffoni, F. Pompeo, G. F. Santori, and N. N. Nichio, "Nickel catalysts applied in steam reforming of glycerol for hydrogen production," Catalysis communications, vol. 10, no. 13, pp. 1656-1660, 2009.
    [59] B. Zhang, X. Tang, Y. Li, Y. Xu, and W. Shen, "Hydrogen production from steam reforming of ethanol and glycerol over ceria-supported metal catalysts," International Journal of Hydrogen Energy, vol. 32, no. 13, pp. 2367-2373, 2007.
    [60] O. A. Sahraei, A. Desgagnés, F. Larachi, and M. C. Iliuta, "A comparative study on the performance of M (Rh, Ru, Ni)-promoted metallurgical waste driven catalysts for H2 production by glycerol steam reforming," International Journal of Hydrogen Energy, vol. 46, no. 63, pp. 32017-32035, 2021.
    [61] K. H. Delgado, L. Maier, S. Tischer, A. Zellner, H. Stotz, and O. Deutschmann, "Surface reaction kinetics of steam-and CO2-reforming as well as oxidation of methane over nickel-based catalysts," Catalysts, vol. 5, no. 2, pp. 871-904, 2015.
    [62] S. Lin, J. Huang, X. Gao, X. Ye, and H. Guo, "Theoretical insight into the reaction mechanism of ethanol steam reforming on Co (0001)," The Journal of Physical Chemistry C, vol. 119, no. 5, pp. 2680-2691, 2015.
    [63] Z.-J. Zuo, L. Wang, P.-D. Han, and W. Huang, "Insights into the reaction mechanisms of methanol decomposition, methanol oxidation and steam reforming of methanol on Cu (111): A density functional theory study," International journal of hydrogen energy, vol. 39, no. 4, pp. 1664-1679, 2014.
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