磷预处理对γ-Al2O3及其负载Ni2P催化剂加氢脱硫性能影响

摘要/Abstract

摘要： 以磷酸二氢铵为磷源对γ-Al2O3进行磷预处理，得到了不同磷质量分数(0~7.2%)的改性γ-Al2O3，以其为载体采用等体积浸渍法和H2原位还原法制备了负载型Ni2P催化剂。以噻吩为模型化合物在固定床反应器上对催化剂的加氢脱硫(HDS)性能进行评价，并运用X射线衍射(XRD)、N2吸附/脱附、氨程序升温脱附(NH3-TPD)等技术对改性载体及催化剂进行表征。结果表明：对γ-Al2O3进行磷预处理可以提高其比表面积，并可以对其孔径分布进行一定的调节；同时，磷的加入可以调变γ-Al2O3的酸强度分布及总酸量。采用适量磷改性的γ-Al2O3为载体制备催化剂有利于生成纯相的Ni2P。当载体中的磷质量分数达到3.6%时，γ-Al2O3的总酸量及中强酸量较高，比表面积较大，以其为载体制备的负载型Ni2P催化剂具有更高的加氢脱硫性能。

Abstract: A series of phosphorus modified γ-Al2O3 supports using diammonium phosphate were prepared by incipient wetness impregnation method. The supported nickel phosphide catalysts based on the modified supports were prepared by incipient wetness impregnation followed by in situ H2 reduction. Their hydrodesulfurization (HDS) performance were evaluated in a continuous flow fixed-bed reactor using thiophene as a model molecule. The obtained phosphorus modified supports and catalysts were characterized by XRD, N2 adsorption-desorption and temperature-programmed desorption of ammonia (NH3-TPD). The results show that the surface area of the phosphorus modified γ-Al2O3 first increases and then declines with increasing of phosphorus content. The pore size distribution, surface acidity and acid strength distribution of the γ-Al2O3 can be effectively adjusted by the addition of phosphorus. Pure phase of Ni2P were easily formed on the phosphorus-containing alumina support after in situ H2 reduction. The amount of medium-strong acid, total amount of acid and catalytic activity are maximum when phosphorus content on the modified γ-Al2O3 is 3.6%.

李素魁王海彦鄢景森. 磷预处理对γ-Al2O3及其负载Ni2P催化剂加氢脱硫性能影响[J]. 石油炼制与化工, 2014, 45(5): 60-65.

参考文献

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[20] 张孔远，韩红亮，周然然，等. 磷改性拟薄水铝石性能及在蜡油加氢催化剂中的应用[J]. 工业催化，2007, 18(2): 37-41.
[21] Oyama S.T, Wang x, Lee Y.K, et al. Effect of phosphorus content in nickel phosphide catalysts studiedby XAFS and other techniques[J]. J. Catal. , 2002, 210(1): 207-217.
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[23] Benson J W, Schrader G L, Angelici R J. Studies of the mechanism of thiophene hydrodesulfurzation(DDS) of thiophene over Pb-Mo2S catalyst [J]. J. Mol. Catal. A: Chem., 1995, 96: 283-299.
[24] 维妮，磷化物催化剂的制备及其加氢脱硫反应性能的研究[D]. 北京: 北京化工大学, 2011.
, [1] Youssef Saih, Kohichi Segaw, Catalytic activity of CoMo catalysts supported on boron-modified alumina for the hydrodesulphurization of dibenzothiophene and 4, 6-dimethyldibenzothiophene[J]. Applied Catalysis A: General, 380 (2010): 149–164.
[2] 刘理华，李广慈，柳云骐，等. Ni2P/SiO2催化剂的制备及加氢脱硫性能[J]. 石油炼制与化工，2011, 42（1）：64-68.
[3] 鄢景森，王安杰，李翔，等. 以SiO2为载体的磷化钼催化剂上喹啉的加氢脱氮反应[J]. 石油学报(石油加工), 2006, 22(3): 1-6.
[4] 孙福侠, 李灿. 过渡金属磷化物的加氢精制催化性能研究进展[J]. 石油学报(石油加工), 2005, 21(6): 1-10.
[5] 马倩, 曾鹏晖, 季生福, 等. 金属助剂对Ni2P/SBA-15催化剂结构及二苯并噻吩加氢脱硫性能的影响[J]. 石油学报(石油加工), 2011, 27(2): 175-180.
[6] 宋华, 张永江, 宋华林, 等. 柠檬酸对Ni2P/TiO2-Al2O3催化剂加氢脱硫性能的影响[J]. 物理化学学报, 2012, 28 (3), 661-666.
[7] Tops?e H，Clausen B S. Active sites and support effects in hydrodesulfurization catalysts[J]. Appl .Catal, 1986, 25(2): 273-293.
[8] 田部浩三.新固体酸和碱及其催化作用[M]. 北京：化学工业出版社，1998. 203-210.
[9] 魏强,周亚松,黄梅梅,等. 磷改性Y 型分子筛的合成与表征[J]. 石油学报(石油加工), 2011, 27(2): 275-279.
[10] Ferdous D, Dalai A K, Adiaye J. A series of NiMo/Al2O3 catalysts containing boron and phosphorous. Paty Ⅰ：Synthesis and character[J]. Appl Catal A: Gen, 2004, 260: 137-151.
[11] 尹海亮，周同娜，刘晨光. 磷对NiMo/Al2O3催化剂活性组分与载体间相互作用的影响[J]. 石油炼制与化工, 2012, 43(7): 32-36.
[12] 周同娜，尹海亮，韩姝娜，等. 不同磷含量NiMoP/γ-Al2O3催化剂活性相结构研究[J]. 燃料化学学报, 2009, 37(3): 330-334.
[13] 曹光伟，罗锡辉，刘振华，等. 加氢处理催化剂的制备与表征Ⅰ.MoNiP/Al2O3催化剂的制备及助剂的作用[J]. 催化学报, 2011, 22(2): 143-147.
[14] Tompsett G A, Krogh L, Griffin D W, et al. Hysteresis and scanning behavior of mesoporous molecular sieves[J]. Langmuir, 2005, 21(18): 8214-8225.
[15] Sawhill S J, Layman K A, Van Wyk D R, et al. Thiophene hydrodesulfurization over nickel phosphide catalysts: Effect of the precursor composition and support[J]. J. Catal. , 2005, 231(2): 300-313.
[16] 杨占林, 彭绍忠, 刘雪玲, 等. P改性对Mo-Ni/γ-Al2O3催化剂结构和性质影响[J]. 石油化工, 2007, 36(8): 784-788.
[17] 李伟, 李生祥, 张明慧, 等. 磷改性TiO2-Al2O3复合载体在超深度加氢脱硫中的应用[J].催化学报，2005,26（9）：755-758.
[18]Pierotti R A, Rouquerol J. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity[J]. Pure Appl. Chem., 1985, 57(4): 603-619.
[19] 唐莉, 孙雪芹, 刘丛华, 等. 磷改性对γ-Al2O3酸性和催化活性的影响[J]．应用化工, 2012, 40(10):1785-1786.
[20] 张孔远，韩红亮，周然然，等. 磷改性拟薄水铝石性能及在蜡油加氢催化剂中的应用[J]. 工业催化，2007, 18(2): 37-41.
[21] Oyama S.T, Wang x, Lee Y.K, et al. Effect of phosphorus content in nickel phosphide catalysts studiedby XAFS and other techniques[J]. J. Catal. , 2002, 210(1): 207-217.
[22] Bianchini C, Meli A, Vizza F. Role of single-site catalysts in the hydrogenation of thiophenes:from models systems to effective HDS catalysts [J]. Journal of Organometallic Chemistry, 2004, 689: 4277-4290
[23] Benson J W, Schrader G L, Angelici R J. Studies of the mechanism of thiophene hydrodesulfurzation(DDS) of thiophene over Pb-Mo2S catalyst [J]. J. Mol. Catal. A: Chem., 1995, 96: 283-299.
[24] 维妮，磷化物催化剂的制备及其加氢脱硫反应性能的研究[D]. 北京: 北京化工大学, 2011.