前驱体焙烧温度对Ni<sub>2</sub>P/SiO<sub>2</sub>月桂酸甲酯脱氧性能的影响

摘要

以负载磷酸镍为前驱体采用程序升温还原法制备了Ni₂P/SiO₂催化剂，采用H₂-程序升温还原（H₂-TPR）、X-射线衍射（XRD）、透射电子显微镜（TEM）、N₂吸附、CO吸附和NH₃-程序升温脱附（NH₃-TPD）等方法研究了前驱体焙烧温度对Ni₂P/SiO₂催化剂结构和月桂酸甲酯脱氧性能的影响。结果表明，随着前驱体焙烧温度从400℃增加到800℃，所制备催化剂的比表面积、孔容先基本不变然后降低，Ni₂P晶粒尺寸增大，催化剂酸性减弱。在月桂酸甲酯脱氧反应中，随前驱体焙烧温度提高，所制备Ni₂P/SiO₂催化剂脱氧活性先升高后降低，其中由在500℃焙烧前驱体所制备的催化剂具有较高脱氧性能；此外，脱氧产物十一烷和十二烷的物质的量之比呈现先基本不变后减小的趋势，说明前驱体焙烧温度对所制备催化剂上脱氧途径有一定影响。影响脱氧途径的主要因素是Ni₂P晶粒尺寸及催化剂酸性。

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	郑征
	赵莎
	陈吉祥

关键词：磷化镍晶粒尺寸焙烧温度加氢脱氧

Abstract：

Ni₂P/SiO₂ was prepared by temperature programmed reduction from SiO₂-supported nickel phosphate. The influence of precursor calcination temperature on the structure and performance of Ni₂P/SiO₂ catalysts for deoxygenation of methyl laurate to undecane and dodecane was investigated by means of H₂-temperature programmed reduction(H₂-TPR), X-Ray diffractions(XRD), transmission electron microscopy(TEM), N₂ adsorption, CO adsorption and NH₃-temperature programmed desorption(NH₃-TPD). With increasing calcination temperatures of the precursors from 400℃ to 800℃, the specific surface area and the pore volume of the Ni₂P/SiO₂ catalyst first remained unchanged and then decreased, Ni₂P crystallite size increased and catalyst acidity decreased. In addition, in the deoxygenation of methyl laurate, the deoxygenation activity of the Ni₂P/SiO₂ catalysts first increased and then decreased. The Ni₂P/SiO₂ catalyst which was prepared from the precursor calcined at 500℃ had higher deoxygenation activity. In addition, the molar ratio of undecane and dodecane did not change obviously at low calcination temperature of precursor and then decreased at high calcination temperature of precursor. The calcination temperature of precursor affected the deoxygenation pathway of methyl laurate on the prepared Ni₂P/SiO₂ catalyst. The deoxygenation pathway is mainly determined by the Ni₂P crystallite size and catalyst acidity.

Keywords： nickel phosphide； crystallite size； calcination temperature； hydrodeoxygenation

Received 2014-05-08;

Fund:

国家自然科学基金（21176177）；天津市自然科学基金（12JCYBJC13200）。

Corresponding Authors: 陈吉祥,E-mail:jxchen@tju.edu.cn。 Email: jxchen@tju.edu.cn

About author: 郑征(1988-),男,硕士研究生,从事应用催化方面的研究。

引用本文:

郑征, 赵莎, 陈吉祥.前驱体焙烧温度对Ni₂P/SiO₂月桂酸甲酯脱氧性能的影响[J]. 化学工业与工程, 2016,33(4): 11-17

Zheng Zheng, Zhao Sha, Chen Jixiang.Influence of Precursor Calcination Temperature on Structure and Performance of Ni₂P/SiO₂ for Deoxygenation of Methyl Laurate[J]. Chemcial Industry and Engineering, 2016,33(4): 11-17

[1] Yang Y, Cristina O H, Víctor A, et al. Ni₂P/SBA-15 as a hydrodeoxygenation catalyst with enhanced selectivity for the conversion of methyl oleate into n-octadecane[J]. Acs Catal, 2012, 2: 592-598
[2] Kubic?ková I, Kubi?ka D. Utilization of triglycerides and related feedstocks for production of clean hydrocarbon fuels and petrochemicals: A review[J]. Waste Biomass Valor, 2010, 1: 293-308
[3] Snåre M, Kubi?ková I, Mäki-Arvela P, et al. Heterogeneous catalytic deoxygenation of stearic acid for production of biodiesel[J]. Ind Eng Chem Res, 2006, 45: 5708-5715
[4] Zuo H, Liu Q, Wang T, et al. Hydrodeoxygenation of methyl palmitate over supported Ni catalysts for diesel-like fuel production[J]. Energy & Fuels, 2012, 26: 3747-3755
[5] Senol O I, Ryymin E M, Viljava T R, et al. Reactions of methyl heptanoate hydrodeoxygenation on sulphided catalysts[J]. J Mol Catal A: Chem, 2007, 268: 1-8
[6] Liu W, He X, Lu C. Researches in the hydrogenation properties of metal nitrides and carbides catalysts[J]. Industrial Catalysis, 2005, 13(3): 1-5
[7] Yang Y, Chen J, Shi H, et al. Deoxygenation of methyl laurate as a model compound to hydrocarbons on Ni₂P/SiO₂, Ni₂P/MCM-41, and Ni₂P/SBA-15 catalysts with different dispersions[J]. Energy & Fuels, 2013, 27: 3400-3409
[8] Yang Y, Cristina O H, Patricia P, et al. Synthesis of nickel phosphide nanorods as catalyst for the hydrotreating of methyl oleate[J]. Top Catal, 2012, 55: 991-998
[9] Oyama S T. Novel catalysts for advanced hydroprocessing: Transition metal phosphides[J]. J Catal, 2003, 216: 343-352
[10] Oyama S T, Gott T, Zhao H, et al. Transition metal phosphide hydroprocessing catalysts: A review[J]. Catalysis Today, 2009, 143: 94-107
[11] Li K, Wang R, Chen J, et al. Hydrodeoxygenation of anisole over silica-supported Ni₂P, MoP, and NiMoP catalysts[J]. Energy & Fuels, 2011, 25: 854-863
[12] Chen J, Shi H, Li L, et al. Deoxygenation of methyl laurate as a model compound to hydrocarbons on transition metal phosphide catalysts[J]. Applied Catalysis B: Environmental, 2014, 144: 870-884
[13] Oyama S T, Lee Y K. The active site of nickel phosphide catalysts for the hydrodesulfurization of 4, 6-DMDBT[J]. J Catal, 2008, 258(2): 393-400
[14] Moula M G, Suzuki S, Chun W J, et al. The first atomic-scale observation of a Ni₂P (0001) single crystal surface[J]. Chem Lett, 2006, 35: 90-91
[15] Moula M G, Suzuki S, Chun W J, et al. Surface structures of Ni₂P(0001)-Scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) characterizations[J]. Surf Interface Anal, 2006, 38(12/13): 1611-1614
[16] Prins R, Bussell M E. Metal phosphides: Preparation, characterization and catalytic reactivity[J]. Catal Lett, 2012, 142: 1413-1436
[17] Oyama S T, Wang X, Lee Y K, et al. Effect of phosphorus content in nickel phosphide catalysts studied by XAFS and other techniques[J]. J Catal, 2002, 210: 207-217
[18] Duan X, Yang T, Wang A. Role of sulfur in hydrotreating catalysis over nickel phosphide[J]. J Catal, 2009, 261: 232-240
[19] Yao N, Chen J, Zhang J, et al. Influence of support calcination temperature on properties of Ni/TiO₂ for catalytic hydrogenation of o-chloronitro-benzene to o-chloroaniline[J]. Catal Commun, 2008, 9: 1510-1516
[20] Zhang X, Zhang Q, Chen L, et al. Effect of calcination temperature of Ni/SiO₂-ZrO₂ catalyst on its hydrode oxygenation of guaiacol[J]. Chin J Catal, 2014, 35: 302-309
[21] Lee Y K, Oyama S T. Bifunctional nature of a SiO₂-supported Ni₂P catalyst for hydrotreating: EXAFS and FTIR studies[J]. J Catal, 2006, 239: 376-389