载体对Ni<sub>2</sub>P催化剂加氢脱氮反应性能的影响

鄢景森; 王海彦; 李素魁; 李晓惠

载体对Ni₂P催化剂加氢脱氮反应性能的影响

鄢景森^1,2,3,
王海彦^1,2,,
李素魁²,
李晓惠³

1.
中国石油大学(华东) 山东青岛 266555;
2.
辽宁石油化工大学, 辽宁抚顺 113001;
3.
辽宁科技学院, 辽宁本溪 117004

详细信息

通讯作者:
王海彦，男，教授，从事石油化工工艺及工业催化的研究，E-mail：fswhy@126.com

中图分类号: O643
计量
- 文章访问数: 973
- HTML全文浏览量: 29
- PDF下载量: 616
- 被引次数: 0
出版历程
- 收稿日期: 2013-08-19
- 修回日期: 2013-10-11
- 刊出日期: 2014-03-31

Effects of support on hydrodenitrogenation activity of nickel phosphide catalysts

1.
China University of Petroleum (East China), Qingdao 266555, China;
2.
Liaoning University of Petro-Chemical Technology, Fushun 113001, China;
3.
Liaoning Institute of Science and Technology, Benxi 117004, China

摘要

摘要: 使用TiO₂、Al₂O₃以及TiO₂-Al₂O₃复合载体考察了载体对磷化镍催化剂活性相和加氢脱氮性能的影响。不同钛铝原子比的TiO₂-Al₂O₃复合载体采用原位-溶胶凝胶法制备，负载的磷化镍催化剂采用等体积浸渍法和H₂原位还原法制备。以喹啉为模型化合物在固定床反应器上对催化剂的加氢脱氮性能进行评价，采用XRD、N₂ 吸附、TEM和H₂-TPR等技术对催化剂和载体进行了表征。结果表明，制成的复合载体基本保留了最初引入的γ-Al₂O₃的孔特征，分散在γ-Al₂O₃表面的TiO₂以锐钛矿晶型存在。不同载体对催化剂的H₂还原行为有显著影响，所形成的活性物种也不相同。Al₂O₃中引入TiO₂可以减弱P物种和Al₂O₃之间的相互作用，有利于Ni₂P活性相的生成和催化活性的提高。当Ti/Al的原子比为1：8时，Ni₂P/TiO₂-Al₂O₃催化剂比Ni₂P/TiO₂、 Ni₂P/Al₂O₃催化剂具有更高的加氢脱氮活性。
- 磷化镍 /
- 二氧化钛 /
- 氧化铝 /
- 复合载体 /
- 加氢脱氮 /
- 喹啉
Abstract: The effects of the support on active site formation and hydrodenitrogenation(HDN) activity of nickel phosphide catalysts were examined, using TiO₂, Al₂O₃ and TiO₂-Al₂O₃, composite supports. A series of TiO₂-Al₂O₃ prepared by hydrolysis and deposition of tetrabutyl titanate on macropore Al₂O₃, and the supported nickel phosphide catalyst, were prepared by incipient wetness impregnation and in situ H₂ reduction method. The samples were characterized by X-ray diffraction(XRD), BET surface area, transmission electron microscopy(TEM) and H₂ temperature-programmed reduction(H₂-TPR).Their hydrodenitrogenation(HDN) performance were evaluated on a continuous-flow fixed-bed reactor by using quinoline as the model molecules. The results showed that the TiO₂-Al₂O₃ composite support still retained the pore properties of macropore Al₂O₃, and TiO₂ were well dispersed on the Al₂O₃ surface in the form of anatase. Different supports have great influence on the reduction behaviour of the oxidic precusors and HDN activity of phosphide catalysts. The main active phase after reduction was Ni₂P phase for the TiO₂ and TiO₂-Al₂O₃ supportd catalyst, but only Ni₁₂P₅ appeared for the Al₂O₃ supported catalyst. The order of HDN activities of nickel phosphide reduced at optimal reaction conditions was TiO₂-Al₂O₃ > Al₂O₃> TiO₂. TiO₂-Al₂O₃ supported catalyst with the Ti /Al atomic ratio of 1:8 exhibited the highest HDN activity among all catalysts. The presence of TiO₂ weakened the strong interaction between the Al₂O₃ and phosphate, and contributed to the formation of Ni₂P active phase and the improvement of HDN activity.
- nickel phosphide /
- titania /
- alumina /
- composite support /
- hydrodenitrogenation /
- quinoline

HTML全文

参考文献(25)

OYAMA S T. Novel catalysts for advanced hydroprocessing: Transition metal phosphides[J]. J Catal, 2003, 216(2): 343-352.

OYAMA S T, GOTT T, ZHAO H Y, LEE Y K. Transition metal phosphide hydroprocessing catalysts: A review[J]. Catal Today, 2009, 143(1/2): 94-107.

CLARK P, OYAMA S T. Alumina-supported molybdenum phosphide hydroprocessing catalysts[J]. J Catal, 2003, 218(1): 78-87.

SUN F X, WU W C, WU Z L, GUO J, WEI Z B, YANG Y X, JIANG Z X, TIAN F P, LI C. Dibenzothiophene hydrodesulfurization activity and surface sites of silica-supported MoP, Ni₂P, and NiMoP catalysts[J]. J Catal, 2004, 228(2): 298-310.

WANG A J, RUAN L F, TENG Y, LI X, LU M H, REN J, WANG Y, HU Y K. Hydrodesulfurization of dibenzothiophene over siliceous MCM-41-supported nickel phosphide catalysts[J]. J Catal, 2005, 229(2): 314-321.

SHU Y, OYAMA S T. Synthesis, characterization, and hydrotreating activity of carbon-supported transition metal phosphide[J]. Carbon, 2005, 43(7): 1517-1532.

KORANYI T I, VíT Z, PODUVAL D G, RYOO R, KIM H C, HENSEN E J M. SBA-15-supported nickel phosphide hydrotreationg catalysts[J]. J Catal, 2008, 253(1): 119-131.

RAMIREZ J, MACIAS G, CEDENO L, GUTIERREZ-ALEJANDRE, A, CUEVAS R, CASTULLO P. The role of titania in supported Mo, CoMo, NiMo and NiW hydrodesulfurization catalysts: Analysis of past and new evidences[J]. Catal Today, 2004, 98(1): 19-30.

DAMYANOVA S, SPOJAKINA A, JIRATIVA K. Effect of mixed titania-alumina supports on the phase composition of NiMo/TiO₂-Al₂O₃ catalysts[J]. Appl Catal A: Gen, 1995, 125(2): 257-269.

鲁墨弘, 王安杰, 李翔, 胡永康, 单玉华. TiO₂的加入对非负载的Ni₂P催化剂加氢脱氮性能的促进作用[J]. 石油学报(石油加工), 2009, 25(4): 522-526. (LU Mo-hong, WANG An-jie, LI Xiang, HU Yong-kang. Effect of TiO₂ addition methods on hydrodenitrogenation performance of nickel phosphide[J]. Acta Petrolei Sinica(Petroleum Processing Section.), 2009, 25(4): 496-502.)

宋华, 于洪坤, 武显春, 郭云涛. TiO₂-Al₂O₃载体的制备及Ni₂P/TiO₂-Al₂O₃催化剂上的同时加氢脱硫和加氢脱氮反应[J]. 催化学报, 2010, 31(4): 447-453. (SONG Hua, YU Hong-kun, WU Xian-chun, GUO Yun-tao. Preparation of TiO₂-Al₂O₃ support and simutaneous hydrodesulfurization and hydrodenitrogenation over Ni₂P/TiO₂-Al₂O₃ catalyst[J]. Chinese Journal of Catalysis, 2010, 31(4): 447-453.)

OYAMA S T, WANG X, LEE Y K, BANDO K, REQUEJO F G. Effect of phosphorus content in nickel phosphide catalysts studied by XAFS and other techniques[J]. J Catal, 2002, 210(1): 207-217.

WANG X, CLARK P, OYAMA S T. Synthesis, characterization, and hydrotreating activity of several iron group transition metal phosphides[J]. J Catal, 2002, 208(2): 321-331.

SCHEFFER B, ARNOLDY P, MOULIJN J A. Sulfidability and hydrodesulfurization activity of Mo catalysts supported on alumina, silica and carbon[J]. J Catal, 1988, 112(2): 516-527.

辛勤, 罗孟飞. 现代催化研究方法[M]. 北京: 科学出版社, 2009: 1-41. (XIN Qin, LUO Meng-fei. Modern catalysis research methods[M]. Beijing: Science Press, 2009: 1-41.)

史媛媛. 载体焙烧温度对氧化铝负载磷化镍结构及HDC 性能的影响[D]. 天津: 天津大学, 2010. (SHI Yuan-yuan. Effect of support calcination temperature on structure and performance of Al₂O₃-supported nickel phosphide catalysts[D]. Tianjin: University of Tianjin, 2010.)

CLARK P A, OYAMA S T. Alumina-supported molybdenum phosphidehydroprocessing catalysts[J]. J Catal, 2003, 218(1): 78-87.

KAO C, TSAI S, BAHL M. Electronic properties, structure and temperature-dependent composition of nickel deposited on rutile titanium dioxide(110) surfaces[J]. Surf Sci, 1980, 95(1): 1-14.

ARMBRUSTER T. Phase relations and exsolution phenomena in the system NiO-TiO₂[J]. Solid State Chem, 1981, 36(3): 275-288.

LI M F, LI H F. Effect of surface characteristics of different alumina on metal-support interaction and hydrodesulfurization activity[J]. Fuel, 2009, 88: 1281-1285.

鲁墨弘.磷化镍催化剂的制备及其加氢脱氮反应性能研究[D].大连: 大连理工大学, 2007. (LU Mo-hong. Preparation and performance of nickel phosphide catalyst for hydrodenitrogenation[D]. Beijing: Dalian University of Technology, 2007.)

曲本连, 柴永明, 相春娥, 张景成, 刘晨光.磷化镍和磷化钼催化剂的原位XRD研究[J].石油学报(石油加工), 2009, 25(4): 496-502. (QU Ben-lian, CHAI Yong-ming, XIANG Chun-e, ZHANG Jing-cheng. In-situ XRD study of nickel phosphide and molebednum phosphide catalysts[J]. Acta Petrolei Sinica(Petroleum Processing Section.), 2009, 25(4): 496-502.

KUMAR S R, PILLAI S C, HAREESH U S, MUKUNDAN P, WARRIER K G K. Synthesis of thermally stable, high surface area anatase-alumina mixed oxides[J]. Mater Lett, 2000, 286: 43-46.

SATTERFIELD C N, COCCHETTO J F. Reaction network and kinetics of the vapor-phase catalytic hydrodenitrogenation of quinoline[J]. Ind Eng Chem Proc Des Dev, 1981, 20(1): 53-62.

JIAN M, PRINS R. Mechanism of the hydrodenitrogenation of quinoline over NiMo(P)/Al₂O₃ catalysts[J]. J Catal, 1998, 179(1): 18-27.

施引文献

资源附件(0)

访问统计